US 20030207962A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2003/0207962 A1 Oya et al. (43) Pub. Date: Nov. 6, 2003
(54) ANTIFOULING COATING COMPOSITION, (57) ABSTRACT COATING FILM THEREFROM, BASE MATERIAL COVERED WITH THE COATING FILM AND ANTIFOULING METHOD An antifouling coating composition comprising (A) a silyl ester copolymer containing constituent units derived from a (76) Inventors: Masaaki Oya, Ohtake-shi (JP); Naoya polymerizable unsaturated carboxylic acid silyl ester; (B) a Nakamura, Ohtake-shi (JP); Makoto carboxylic acid, (C) a bivalent or trivalent metal compound; Tsuboi, Ohtake-shi (JP) and (D) a dehydrating agent. It is preferred that the com ponent (C) be contained in an amount of 1.2 equivalents or Correspondence Address: more, in terms of the number of equivalents of metal as a Leonard W. Sherman constituent of the component (C), per equivalent of carboxyl Sherman & Shalloway group of the carboxylic acid (B); that the component (C) be 413 N. Washington Street a bivalent metal compound; and that the component (C) be Alexandria, VA 22314 (US) a compound of at least one metal Selected from the group consisting of Zinc, copper, magnesium, calcium and barium. (21) Appl. No.: 10/375,005 From the antifouling coating composition, there can be obtained an antifouling coating film which exhibits leSS (22) Filed: Feb. 28, 2003 cracking tendency, excellent adherence So as to ensure leSS (30) Foreign Application Priority Data peeling tendency and desirably controlled hydrolysis rate So as to be excellent in antifouling performance, in particular, Mar. 6, 2002 (JP)...... 2002-60696 antifouling properties in highly fouling environment and long-term antifouling properties. With respect to the pro Publication Classification Vided antifouling coating composition, its Storage Stability is high, its concentration can be increased, the amount of (51) Int. Cl...... B05D 3/02; CO8K 3/00 Solvent used therefor can be reduced, and its applicability is (52) U.S. Cl...... 523/177; 427/385.5; 523/122 high. US 2003/0207962 A1 Nov. 6, 2003
ANTIFOULING COATING COMPOSITION, and tributyltin halides (BuSnX wherein X is a halogen COATING FILM THEREFROM, BASE MATERIAL atom), So that an antifouling effect is exerted. Furthermore, COVERED WITH THE COATING FILM AND the copolymer hydrolyzate per se is a “hydrolyzable self ANTIFOULING METHOD polishing paint' which is rendered water-Soluble and thus is dissolved in the Seawater, So that no resin residue is left on FIELD OF THE INVENTION the surface of the ship bottom coating with the result that 0001. The present invention relates to an antifouling always an active Surface can be maintained. coating composition which contains a silyl ester copolymer, 0006. However, the above organotin compounds are so an antifouling coating film formed from the antifouling highly toxic that apprehensions are being entertained with coating composition, an antifouling method wherein the respect to marine pollution, occurrence of anomalous fish antifouling coating composition is used, and a marine vessel and anomalous shellfish and adverse effects on ecosystem (hull) or underwater structure covered with the coating film. through food chain. Therefore, the development of a non 0002 More particularly, the present invention relates to Stannic antifouling paint is desired as a Substitute therefor. an antifouling coating composition which can be formed 0007 For example, antifouling paints based on silyl into an antifouling paint whose Storage Stability is excellent esters as described in Japanese Patent Laid-open Publication and wherein the amount of Solvent used can be reduced due Nos. 4(1992)-264170 (reference (a)), 4(1992)-264169 (ref to low Viscosity. From the antifouling paint, there can be erence (b)) and 4(1992)-264168 (reference (c)) can be obtained an antifouling coating film which exhibits leSS mentioned as the above nonstannic antifouling paint. How cracking tendency, excellent adherence So as to ensure leSS ever, these antifouling paints have Such problems that not peeling tendency and desirably controlled hydrolysis rate So only are their antifouling capabilities poor but also cracking as to be excellent in antifouling performance (antifouling and peeling are likely to occur as pointed out in Japanese activity), in particular, antifouling properties in Stationary Patent Laid-open Publication Nos. 6(1994)-157941 (refer environment or highly fouling environment and long-term ence (d)) and 6(1994)-157940 (reference (e)). antifouling properties. Further, the present invention relates 0008 Further, Japanese Patent Laid-open Publication to an antifouling coating film formed from the antifouling No. 2(1990)-196869 (reference (f)) teaches, for example, an coating composition, an antifouling method wherein the antifouling paint comprising a blocked acid-functionality antifouling coating composition is used, and a hull or copolymer (A) which is obtained by copolymerizing trim underwater Structure covered with the coating film. ethylsilyl methacrylate, ethyl methacrylate and methoxy ethyl acrylate in the presence of an azo polymerization BACKGROUND OF THE INVENTION initiator and which contains a triorganosilyl carboxylate 0.003 Ship bottoms, underwater structures, fishing nets ester group, namely, a carboxylic acid group blocked with a and the like are likely to have their appearance and function trimethylsilyl group; a polycationic compound (B) which is damaged by the adhesion to Surface and propagation of an organic-Solvent-Soluble Salt of polyvalent metal; and a various aquatic organisms including animals. Such as Shell biocide. In the use of this antifouling paint, for example, the fishes, hard-shelled mussels and barnacles, plants Such as trimethylsilyl group blocking the carboxylic acid group is laver (Seaweeds) and bacteria which is caused when they are Split off by water contained in the paint, and the polyvalent exposed to water for a prolonged period of time. cation reacts with thus formed carboxylic acid group of the acid-functionality copolymer (A), thereby effecting a 0004. In particular, when such an aquatic organism crosslinking and hardening. However, in this reference, adheres to a ship's bottom and propagates, it may occur that there is no description with respect to a method of coping the Surface roughness of the ship as a whole is increased to with water produced by, for example, adding a carboxylic thereby lower the speed of the ship and increase the fuel acid and Zinc white (Zinc oxide) to the paint. Further, the consumed by the ship. Removing the aquatic organism from antifouling paint poses Such a problem that when a free acid the ship bottom necessitates Spending of extensive labor and remains in the antifouling paint, the antifouling paint loaded working time. Also, when bacteria adhere to, for example, with a component which reacts with a free acid to thereby an underwater Structure and propagate and, further, Slime produce water, there occur, for example, gelation and thick (sludgy matter) adheres thereto to cause putrefaction, or ening causing deterioration of Storage Stability, deterioration when a large Sticky organism adheres to the Surface of an of performance, etc. Still further, there is such a problem that underwater Structure, for example, Steel Structure and propa when the acid-functionality copolymer (A) is hydrolyzed gates to thereby damage the coating for corrosion prevention and when a crosslinking reaction occurs between thus provided on the underwater Structure, there is the danger that formed acid group and the polycation, the elution (leaching) damageS Such as deterioration of the Strength and function of of the acid-functionality copolymer (A) would be Sup the underwater Structure and thus marked Shortening of the pressed to result in deterioration of the abradability of life thereof are invited. coating film and deterioration of long-term antifouling capa 0005. It is common practice to apply, for example, a bility. composition comprising a copolymer of tributyltin meth acrylate and methyl methacrylate or the like and cuprous 0009 Thus, the antifouling paint described in the above oxide (Cu2O) as an antifouling paint having excellent anti reference has poor Storage Stability, and the coating film fouling properties to Ship bottoms, etc. So as to avoid the obtained from the antifouling paint has a drawback in that above damages. This copolymer of the antifouling paint is the cracking resistance thereof is not fully Satisfactory. hydrolyzed in the Seawater to thereby liberate organotin 0010) Published Japanese Translation of PCT Patent compounds such as bistributyltin oxide (tributyltin ether of Applications from Other States, No. 60(1985)-500452 (ref the formula BuSn-O-SnBu wherein Bu is a butyl group) erence (g)) and Japanese Patent Laid-open Publication No. US 2003/0207962 A1 Nov. 6, 2003
63(1988)-215780 describe a resin for antifouling paint 0014) wherein each of R to R represents the same which is obtained by copolymerizing a vinyl monomer group as represented by R' to R or a group of the having an organosilyl group, Such as a trialkylsilyl ester of formula (b), (meth)acrylic acid, with another vinyl monomer and which has a number average molecular weight of 3000 to 40,000. 0015) provided that m groups represented by R and It is further described that the resin can be blended with an R may be identical with or different from each organic water coupler Such as trimethyl orthoformate, an other). As the Surfactant, there are mentioned, for antifouling agent Such as cuprous oxide and a pigment Such example, a fatty acid of -5° C. or higher melting as red iron oxide. However, as described in the above point having 8 or more carbon atoms and an ester Japanese Patent Laid-open Publication No. 6(1994)-157940 thereof. It is described that because the polymer A (reference (e)), this resin for antifouling paint has drawbacks and copolymer AB contained in the coating compo in that it is likely to gel during the Storage thereof and that Sition are hydrolyzed in the presence of water, it is the coating film formed from the antifouling paint is poor in desirable to, before forming the coating composition cracking and peeling resistances. into a paint, add thereto a water coupler for trapping water contained in the antifouling agent and the 0011 Japanese Patent Publication No. 5(1993)-32433 pigment. AS the water coupler, there are mentioned corresponding to the above Published Japanese Translation triethyl orthoformate, tetraethyl silicate ((CHO of PCT Patent Applications from Other States, No. ),Si), etc. (In the corresponding Japanese Patent No. 60(1985)-500452 (reference (g)) discloses an antifouling 2775862, the water coupler is described as an essen paint comprising a poison (a) and a polymer binder (b) tial component.) having a repeating unit of the formula -CH-CX (COOR)-(B)- (wherein X is H or CH, R is SiR's or 0016. In this coating composition, the source of water is Si(OR), in which R' is an alkyl group, etc. and B is an not limited to the antifouling agent and pigment mentioned ethylenically unsaturated monomer residue), which polymer above, and water is also produced by a reaction between a binder has a specified hydrolysis rate. Further, it is described fatty acid and a pigment, e.g., Zinc oxide (ZnO). Thus, in the that the antifouling paint can contain a Solvent, a water coating composition described in this reference, water may Sensitive pigment component, an inert pigment, a filler and be produced during the preparation thereof (during the a retarder. However, the coating film obtained from the formation into paint). However, a hydrolyzable ester com antifouling paint described in this reference has a drawback pound or ether compound as the water coupler, after in that its cracking resistance is poor. hydrolysis, forms an alcohol. When the polymer has a silyl ester structure, not only is there the possibility of formation 0.012 Japanese Patent Laid-open Publication No. of a polycarboxylic acid through transesterification but also 3(1991)-31372 (having matured to Japanese Patent No. dehydration condensation with a Silanol produced as a 2775862, reference (h)) discloses a coating composition for by-product by hydrolysis occurs to thereby form an alkox preventing the attachment of organisms, comprising a poly ySillyl compound, So that the possibility of new water for mer of monomer A and/or a copolymer AB from the mono mation is high. Therefore, there is Such a problem that the mer A and a vinyl polymerizable monomer B which is Storage Stability of the coating composition is poor, and that copolymerizable with the monomer A, an antifouling agent the coating film obtained therefrom is poor in long-term and a Surfactant. The monomer A is represented by the antifouling properties. formula CH=C(X)—C(=O)—OR (I) (wherein X is Hor -CH, and R is an organic group represented by the 0017 Japanese Patent Laid-open Publication No. formula: 6(1994)-340511 (reference (i)) discloses a marine organism antifouling agent containing a metal Salt of organic acid whose Solubility in water falls within a specified range. AS the organic acid, there is mentioned a Saturated aliphatic R4 R1 (a) monocarboxylic acid having 7 to 10 carbon atoms. AS the metal for constituting the metal Salt of organic acid, there are -CH (Si-O). Si-R2 mentioned metals belonging to Groups Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb, VIa, VIb, VIIa and VIII of the periodic table, Such as Cu, Zn and Ni. 0013 wherein n is 0 or 1; m is a real number of 0 or 0018 Further, it is described that in the use of the marine greater; each of R to R represents a group Such as organism antifouling agent, the antifouling agent can be an alkyl, an alkoxyl or phenyl; and each of RandR dissolved in a vehicle, Such as an oil based varnish or a represents the same group as represented by R' to R chlorinated rubber based resin varnish, before the use. or a group Selected from organosiloxane groups of 0019 However, in this reference, there is no description the formula: teaching or Suggesting a mode wherein a Sillyl ester copoly mer containing constituent units derived from a polymeriZ able unsaturated carboxylic acid Silyl ester is employed as a (b) coating film forming component. Actually, even if only this metal salt (marine organism antifouling agent) is added to a silyl ester copolymer, the obtained antifouling coating com position poses a problem of poor Storage Stability. 0020 Japanese Patent Laid-open Publication No. 7(1995)-18216 (reference (j)) discloses a coating composi US 2003/0207962 A1 Nov. 6, 2003 tion comprising as principal components a polymer (A) from fumaroyloxy group), and monomer B represented by the an organosilicon-containing monomer A having in its mol formula Y-(CH2CH2O)n-R" (wherein R' represents an ecule a triorganosilicon ester group represented by the alkyl or an aryl group, Y represents an acryloyloxy or a formula-COO-SiRRR (I) (wherein each of R, R and methacryloyloxy group, and n is an integer of 1 to 25). AS R is, for example, an alkyl group having 1 to 18 carbon the antifouling agent, there are mentioned in organic com atoms) and copper or a copper compound (B), which coating pounds Such as cuprous oxide, copper powder and other composition contains as an essential component other than copper compounds, Zinc Sulfate and Zinc oxide, and further the components (A) and (B) a Silicon compound having an mentioned organometallic compounds Such as OXine copper alkoxy group represented by the formula: and other organocopper compounds, organonickel com pounds, and Zinc pyrithione and other organozinc com pounds. However, the paint described in this reference has a (C) drawback in that it is inferior in antifouling properties, R5 especially, antifouling properties in Stationary environment or highly fouling environment. it (- R7 0025 Japanese Patent Laid-open Publication No. k 8(1996)-199095 (reference (1)) discloses a coating compo Sition comprising as essential components an antifouling agent and a copolymer obtained from a monomer mixture 0021 (wherein each of R" to R' represents, for example, containing the above monomer A represented by the formula a hydrogen atom, or an alkoxy group or cycloalkoxy group X-SiR'R'R' (1) described in Japanese Patent Laid-open having 1 to 18 carbon atoms; R represents, for example, an Publication No. 7(1995)-102193 and monomer B repre alkyl group having 1 to 18 carbon atoms, and n is an integer sented by the formula Y-(CH(R'))–(OR) (2) (wherein of 1 to 3). In this reference, it is described that a copolymer R represents an alkyl group; R represents an alkyl or a AB from the above monomer A having the group repre cycloalkyl group; and Y represents an acryloyloxy, a meth Sented by the formula (I) and a vinyl monomer copolymer acryloyloxy, a maleinoyloxy or a fumaroyloxy group), izable therewith B may be contained in the coating compo optionally together with a vinyl monomer C copolymeriZ Sition. As the monomer B, there are mentioned (meth)acrylic able with the monomers A and B. As the vinyl monomer C, esterS Such as methyl (meth)acrylate, ethyl (meth)acrylate there are mentioned, for example, acrylic esters, methacrylic and dimethylaminoethyl (meth)acrylate. As the above cop esters, Styrene and Vinyl acetate. Moreover, as the antifoul per or copper compound (B), there are mentioned copper ing agent, there are mentioned inorganic compounds Such as powder, copper naphthenate, etc. As the above silicon com cuprous oxide, copper powder and other copper compounds, pound having an alkoxy group (C), there are mentioned Zinc Sulfate and Zinc oxide, and further mentioned organo tetraethoxysilane, tetra-n-butoxysilane and the like. Further metallic compounds Such as OXine copper and other orga more, it is described that a pigment Such as Zinc oxide, a nocopper compounds, organonickel compounds, and Zinc resin Such as roSin, etc. may be contained in the coating composition. pyrithione and other organozinc compounds. 0026 Japanese Patent Laid-open Publication No. 0022. However, this silicon compound having an alkoxy 8(1996)-269388 (reference (m) discloses a coating compo group (C), when water is present in the paint, induces a Sition comprising, as essential components, bis(2-pyridi hydrolytic reaction with the water to thereby become an nethiol-1-oxide) copper salt (copper pyrithione) and a alcohol. Thus, an adverse influence on an increase of water copolymer obtained from a monomer mixture containing in the paint and coating film is apprehended. Moreover, the monomer A represented by the formula X-SiR'R'R' (1) Silanol after the hydrolysis poses Such a problem that Silanol (wherein R, R and Rall represent a hydrocarbon group molecules undergo a condensation reaction to thereby repro having 1 to 20 carbon atoms and may be identical with or duce water. different from each other, and X represents an acryloyloxy, 0023. In this reference, there is no particular description a methacryloyloxy, a maleinoyloxy, a fumaroyloxy or an it teaching or Suggesting an antifouling coating composition aconoyloxy group), and monomer B represented by the wherein a Sillyl ester copolymer, a carboxylic acid, a bivalent formula Y-(CH2CH2O)n-R" (2) (wherein R" represents an or trivalent metal compound and a dehydrating agent are alkyl or an aryl group; Y represents an acryloyloxy, a employed in combination. The coating film obtained from methacryloyloxy, a maleinoyloxy, a fumaroyloxy or an it the coating composition as particularly described in this aconoyloxy group; and n is an integer of 1 to 25). For reference has a drawback in that it is inferior in cracking example, dimethyl-t-butylsilyl acrylate is mentioned as the resistance and antifouling properties, especially, antifouling monomer A. AS the antifouling agent, there are mentioned properties in Stationary environment or highly fouling envi inorganic compounds Such as cuprous oxide, copper powder and other copper compounds, Zinc Sulfate and Zinc oxide, rOnment. and further mentioned organometallic compounds Such as 0024 Japanese Patent Laid-open Publication No. Oxine copper and other organocopper compounds, organon 7(1995)-102193 (reference (k)) discloses a coating compo ickel compounds, and Zinc pyrithione and other organozinc Sition comprising as essential components an antifouling compounds. Furthermore, for example, rosin and roSin agent and a copolymer obtained from a monomer mixture derivatives are mentioned as an elution rate regulator which containing monomer A represented by the formula can be added to the coating composition. However, with X-SiRRR (wherein R, R and R all represent a group respect to the coating film from the paint described in this Selected from among alkyl and aryl groupS and may be reference, the antifouling properties in Stationary environ identical with or different from each other, and X represents ment are not Satisfactory, and there is room for further an acryloyloxy, a methacryloyloxy, a maleinoyloxy or a improvement to, for example, the Storage Stability of paint. US 2003/0207962 A1 Nov. 6, 2003
0.027 Japanese Patent Laid-open Publication No. acrylate (TBSA), diethylaminoethyl methacrylate 8(1996)-269389 (reference (n)) discloses a coating compo (DEAEMA) and methyl methacrylate (MMA), and a Sition comprising an antifouling agent and a copolymer from copolymer from tri-n-butylsilyl acrylate (TBSA), N,N-dim a monomer mixture containing an unsaturated monomer A ethylacrylamide (DMAA) and methyl methacrylate (MMA). having a triorganosilyl group and a monomer B represented 0039 Still further, as a component which can be added to by any of the following formulae (2) to (9). the coating composition, there are mentioned the same 0028. The monomer B can be: antifouling agents as described in the above Japanese Patent 0029 monomer having a tertiary amino group, rep Laid-open Publication No. 8(1996)-269388. resented by the formula CH2=CRCOOR-NRR7 0040 Japanese Patent Laid-open Publication No. (2) (wherein R' represents H or CH; R represents 8(1996)-269390 (reference (o) discloses a coating compo an alkylene group; and R and R7 represent alkyl Sition comprising: groups and maybe identical with or different from 0041 a polymer from monomer A represented by each other), the formula X-SiR'R'R' (1) (wherein R, R and 0030 monomer containing a quaternary ammonium R all represent groupS. Selected from among alkyl Salt, represented by the formula and aryl groups and may be identical with or differ CH=CRCOOR NR'R'R''(Y) (3) (wherein ent from each other, and X represents an acryloyloxy, R represents H or CH; R represents an alkylene a methacryloyloxy, a maleinoyloxy, a fumaroyloxy group; R' to R' represent alkyl groups and maybe or an itaconoyloxy group), identical with or different from each other; and Y represents a halogen atom), 0042 a polymer from monomer B represented by the formula Y-(CHCHO)n-R" (2) (wherein R' 0031 monomer containing a nitrogen-containing represents an alkyl or an aryl group; Y represents an heterocycle, represented by the formula acryloyloxy, a methacryloyloxy, a maleinoyloxy, a CH=CH-Z (4) (wherein Z represents a group fumaroyloxy or an itaconoyloxy group; and n is an comprising a nitrogen-containing heterocycle), integer of 1 to 25), and an antifouling agent. As the 0032 monomer having in its molecule an alkoxy antifouling agent, there are mentioned the same group or an aryloxyalkylene glycol group, repre antifouling agents as described in the above Japanese Sented by the formula Patent Laid-open Publication No. 8(1996)-269388. CH2=CRCOO(R'O)m(RO)n(RO)o-R7 (5) Further, as a component which can be added to the (wherein R' represents H or CH3; R' represents an coating composition, there are mentioned, for ethylene group; R' represents an alkylene group example, resins Such as rosin and antisetting agents. having 3 carbon atoms; R' represents an alkylene However, with respect to the coating film from the group having 4 carbon atoms; R represents an alkyl coating composition described in this reference, group or aryl group; and each of m, n and o is an there is room for further improvement to the anti integer of 0 or greater, provided that n and o are not fouling properties in Stationary environment, and Simultaneously 0), there is room for improvement to the Storage Stability 0033 (meth)acrylamide represented by the formula of paint. CH=CR''CONR'R' (6) (wherein R represents 0043. Japanese Patent Laid-open Publication No. H or CH; and R'' and R' represent alkyl groups 8(1996)-277372 (reference (p)) discloses a coating compo and may be identical with or different from each Sition comprising a triphenylboron pyridine complex and a other), copolymer from a monomer mixture containing the mono 0034) (meth)acrylamide having a nitrogen-contain mer A represented by the formula X-SiRRR (1) ing cyclic hydrocarbon group, represented by the described in the above Japanese Patent Laid-open Publica formula CH=CRCON()Q (7) (wherein R rep tion No. 8 (1996)-269388 (reference (m)) and the monomer resents H or CH, and N()Q is a nitrogen-containing B represented by the formula Y-(CHCHO)n-R" (2) group wherein, for example, O, N or S may be described in the same reference, wherein the resin compo nent and marine organism adhesion inhibitor consist only of contained in Q), a nonmetallic polymer and an on metallic organic inhibitor, 0035 (meth)acrylic ester containing a furan ring, respectively. Further, for example, rosin and rosin deriva represented by the formula tives are mentioned as an elution rate regulator which can be CH=CRCOOCH-T (8) (wherein R repre added to the coating composition. However, with respect to Sents H or CH, and T represents a furan ring or a the coating film from the coating composition described in tetrahydrofuran ring), or this reference, the antifouling properties in Stationary envi ronment are not satisfactory, and there is room for improve 0.036 monomer of the formula CH=CH-CN (9). ment to the Storage Stability of paint. 0037. Further, as an optional component copolymerizable with the above monomers A and B, there are mentioned 0044) Japanese Patent Laid-open Publication No. various copolymerizable monomerS Such as acrylic acid, 10(1998)-30071 (reference (q)) discloses a coating compo ethyl acrylate, 2-hydroxyethyl (meth)acrylate and 2-hydrox Sition comprising at least one rosin compound (A) consisting of roSin, a rosin derivative or a rosin metal Salt, a polymer ypropyl (meth)acrylate. having an organosilyl ester group (B) consisting of a poly 0.038. In the Example portion of the reference, there are mer from at least one monomer M represented by the mentioned, for example, a copolymer from tri-n-butylsilyl formula X-SiRRR (1) (wherein R to R all represent US 2003/0207962 A1 Nov. 6, 2003 groupS Selected from among alkyl and aryl groupS and may be identical with or different from each other, and X repre Sents an acryloyloxy, a methacryloyloxy, a maleinoyloxy, a fumaroyloxy, an itaconoyloxy or a citraconoyloxy group), R1 R2 (1) and/or a polymer from the above at least one monomer M CH=C-COOSi-R3 and at least one other polymerizable monomer, and an antifouling agent (C). As the antifouling agent, there are R2 mentioned a wide variety of organic and inorganic antifoul ing agents, Such as Zinc oxide and copper naphthenate, which are the same as described in the above Japanese (0.049) wherein R represents H or CH, and each of R, Patent Laid-open Publication No. 8(1996)-269388. Further, RandR' independently represents a group selected from the as components which can be added to the coating compo group consisting of an alkyl group having 1 to 18 carbon Sition, there are mentioned, for example, pigments, water atoms, a cycloalkyl group and an aryl group. couplers, chlorinated paraffin and antisetting agents. 0050 Japanese Patent Laid-open Publication No. 0.045. However, with respect to the paints and coating 11(1999)-343451 (reference (Zd)) discloses an antifouling films disclosed in these references (k) to (q), the paints coating composition comprising a copolymer from a mono exhibit unsatisfactory Storage Stability, and the coating films mer having a triorganosilyl group, represented by the for are unsatisfactory in a balance of cracking resistance, peel mula (2) given below, and another ethylenically unsaturated ing resistance (adherence of coating film), antifouling per monomer which is copolymerizable with the above mono formance, in particular, antifouling properties in Stationary mer; a carboxyl group-containing monobasic acid; and a environment, long-term antifouling properties and Self-pol metal-containing antifouling agent. ishing properties. 0046. Further, for example, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are mentioned as a copolymeriZ H H R1 (2) able optional component in Japanese Patent Publication No. HOOC-C=C-COOSi-R2 5(1993)-82865 (reference (r)). Still further, silyl (meth)acry late copolymers are described in Japanese Patent Laid-open Publication No. 9(1997)-48947 (reference (s)), Japanese Patent Laid-open Publication No. 9(1997)-48948 (reference (t)), Japanese Patent Laid-open Publication No. 9(1997)- 0051 wherein each of R, R and R independently 48949 (reference (u)), Japanese Patent Laid-open Publica represents a group Selected from the group consisting of an tion No. 9(1997)-48950 (reference (v)), Japanese Patent alkyl group having 1 to 18 carbon atoms, a cycloalkyl group Laid-open Publication No. 9(1997)-48951 (reference (w)), and an aryl group. Japanese Patent Publication No. 5(1993)-32433 (reference 0.052 Japanese Patent Laid-open Publication No. 2000 (x)), U.S. Pat. No. 4,593,055 (reference (y)), Japanese Patent 63737 (reference (Ze)) discloses an antifouling coating com Laid-open Publication No. 2(1990)-1968669 (reference (z)) position comprising a copolymer from a monomer having a and WO 91/14743 (reference (za)) However, with respect to triorganosilyl group, represented by the above formula (1), the antifouling paints from the copolymerS described in and another ethylenically unsaturated monomer which is these references (r) to (za), there is room for further copolymerizable with the above monomer; a metallic Soap improvement to the Storage Stability thereof, and to, regard of carboxyl group-containing monobasic acid; and a metal ing the coating films therefrom, the balance of cracking containing antifouling agent. resistance, peeling resistance (adherence of coating film), antifouling performance, in particular, antifouling properties 0053. However, with respect to the antifouling coating in Stationary environment and highly fouling environment, compositions described in these references (Zc) to (Ze), the long-term antifouling properties and Self-polishing proper Storage Stability thereof is not Satisfactory, and lowering of ties. the paint viscosity is so difficult that the use of much solvent has been inevitable. In particular, recently, there has been the 0047 Japanese Patent Laid-open Publication No. problem that although it is demanded to reduce the amount 63(1988)-215780 (reference (zb)) describes copolymers of Solvent added to a coating composition taking environ formed using, for example, methyl methacrylate, n-butyl mental pollution into account, it is difficult to prepare a paint methacrylate and acrylamide as copolymerization compo of low Solvent content from the antifouling coating compo nents, and further describes antifouling paints containing the Sitions described in the references (Zc) to (Ze). above copolymers and cuprous oxide. However, these anti fouling paints have the same drawbacks as those of the OBJECT OF THE INVENTION antifouling paints of the above references. 0054 The present invention has been made with a view 0.048 Japanese Patent Laid-open Publication No. toward solving the above problems of the prior art. It is an 11(1999)-335619 (reference (Zc)) discloses an antifouling object of the present invention to provide an antifouling coating composition comprising a copolymer from a mono coating composition capable of forming an antifouling coat mer having a triorganosilyl group, represented by the for ing film which exhibits less cracking tendency, excellent mula (1) given below, and another ethylenically unsaturated adherence So as to ensure less peeling tendency and desir monomer which is copolymerizable with the above mono ably controlled hydrolysis rate so as to be excellent in mer; a carboxyl group-containing monobasic acid; and a antifouling performance (antifouling activity), in particular, metal-containing antifibuling agent. antifouling properties in highly fouling environment and US 2003/0207962 A1 Nov. 6, 2003
long-term antifouling properties, which antifouling coating ated carboxylic acid silyl ester include constituent units composition is excellent in Storage Stability, can have high derived from a silyl (meth)acrylate which are represented by concentration, can reduce the amount of Solvent used therein the formula: and is excellent in applicability (uniform thick film can be formed by one coating operation). 0055. It is another object of the present invention to (I) provide an antifouling coating film formed from the above CH2 antifouling coating composition, an antifouling method wherein the antifouling coating composition is used, and a CRCOOSiRRR hull or underwater Structure covered with the coating film.
SUMMARY OF THE INVENTION 0067 wherein R represents hydrogen or a methyl group; 0056. The antifouling coating composition of the present and R, R and R' may be identical with or different from invention comprises: each other, and each thereof represents any of a hydrogen 0057 (A) a silyl ester copolymer containing con atom, an alkyl group, a cycloalkyl group, a Substituted or Stituent units derived from a polymerizable unsatur unsubstituted phenyl group and an alkylsilyloxy group. ated carboxylic acid silyl ester, 0068. In the present invention, it is preferred that in the 0.058 (B) a carboxylic acid, formula (I), R represent a branched alkyl group or a cycloalkyl group. 0059 (C) a bivalent or trivalent metal compound (reactive with the carboxylic acid (B)), and 0069. In the present invention, preferably, the silyl ester copolymer (A) contains constituent units (a) derived from a 0060 (D) a dehydrating agent. polymerizable unsaturated carboxylic acid silyl ester and 0061. In the present invention, it is preferred that the constituent units (b) derived from a (meth)acrylate having a bivalent or trivalent metal compound (C) be contained in an polar group. amount of 1.2 equivalents or more, in terms of the number of equivalents of metal as a constituent of the bivalent or 0070 The constituent units (b) derived from a (meth trivalent metal compound (C), per equivalent of carboxyl )acrylate having a polar group are preferably constituent group of the carboxylic acid (B). units represented by the formula: 0.062. In the present invention, it is also preferred that the bivalent or trivalent metal compound (C) be a bivalent metal (II) compound, and that the bivalent or trivalent metal com pound (C) be a compound of at least one metal Selected from CH2 the group consisting of Zinc, copper, magnesium, calcium and barium. 0.063. In the present invention, further, it is preferred that the carboxylic acid (B) be a resin acid or resin acid deriva tive containing at least one carboxylic acid Selected from the 0071) wherein R represents a hydrogen atom or a group consisting of abietic acid, dehydroabietic acid, dihy methyl group; and Z represents an oxygen atom or a droabietic acid, tetrahydroabietic acid, noragathic acid, aga group of the formula -NR", provided that: thenedicarboxylic acid, an agathenedicarboxylic acid monoalkyl ester, Secodehydroabietic acid and isomers 0072 when Z is an oxygen atom, R represents a thereof. Substituted or unsubstituted hydroxyalkyl group, hydroxycycloalkyl group, polyalkylene glycol group 0064. Alternatively, it is preferred that the carboxylic of the formula -(RO)nH (wherein R represents an acid (B) be at least one organic acid (excluding the resin alkylene group, and n is an integer of 2 to 50) or acid) Selected from the group consisting of isononanoic acid, alkoxypolyalkylene glycol group of the formula Versatic acid, naphthenic acid, oleic acid, linoleic acid, -(RO)nR' (wherein R* represents an alkylene linolenic acid, tall oil fatty acid and Soybean oil fatty acid. group, R represents an alkyl group, and n is an 0065. In the present invention, preferably, the dehydrat integer of 1 to 100), and ing agent (D) is an inorganic dehydrating agent. Further, it 0.073 when Z is a group of the formula -NR, R7 is preferred that the dehydrating agent (D) be contained in an represents an alkyl group unsubstituted or Substi amount of 0.15 to 50 equivalents per equivalent of carboxyl tuted with any of a halogen, a hydroxyl group, an group of the carboxylic acid (B). amino group, a Substituted amino group, an acyl 0.066. In the present invention, it is preferred that the group and an alkoxy group, and R represents a constituent units (a) derived from a polymerizable unsatur hydrogen atom. US 2003/0207962 A1 Nov. 6, 2003
0.074. In the present invention, preferably, the silyl ester 0082 In the present invention, the antifouling coating copolymer (A) is a copolymer containing: composition may further comprise an elution accelerating 0075 silyl (meth)acrylate constituent units (a-1) component (G). represented by the formula: 0083. The antifouling coating film of the present inven tion is characterized in that it is formed from any of these antifouling coating compositions. (I-a) 0084. The marine vessel, underwater structure, fishing CH2 gear and fishing net according to the present invention are characterized in that they each have a Surface covered with CR 10COOSiR11R12R 13 the antifouling coating film formed from any of these antifouling coating compositions. 0085. The method of rendering antifouling a marine 0076 wherein R" represents a hydrogen atom or a vessel, an underwater Structure, a fishing gear or a fishing net methyl group; each of R'' and R' independently according to the present invention comprises applying any represents a linear alkyl group having 1 to 10 carbon of these antifouling coating compositions to a Surface of atoms, or a Substituted or unsubstituted phenyl group base material of a marine vessel, an underwater Structure, a or trimethylsilyloxy group; and R' represents a fishing gear or a fishing net and drying the applied antifoul cyclic or acyclic, branched or unbranched alkyl ing coating composition So that a formed antifouling coating group having 1 to 18 carbon atoms, or a Substituted film covers the base material Surface. or unsubstituted phenyl group having 6 to 10 carbon 0086 The present invention provides an antifouling coat atoms or trimethylsilyloxy group, and ing composition which ensures an excellent Storage Stability 0077 silyl (meth)acrylate constituent units (a-2) of paint, and from which there can be obtained an antifoul represented by the formula: ing coating film that exhibits less cracking tendency, excel lent adherence So as to ensure leSS peeling tendency and desirably controlled hydrolysis rate so as to be excellent in (I-b) antifouling performance (antifouling activity), in particular, antifouling properties in Stationary environment or highly CH2 fouling environment and long-term antifouling properties, CR10COOSiR1R15R 16 the antifouling coating film further being excellent in a balance of these characteristics.
DETAILED DESCRIPTION OF THE 0078 wherein R' represents a hydrogen atom or a INVENTION methyl group; each of R'' and R' independently 0087. The antifouling coating composition of the present represents a branched alkyl or cycloalkyl group having 3 to 10 carbon atoms; and R' represents a invention will be described in detail below. linear alkyl group having 1 to 10 carbon atoms, a 0088. The antifouling coating composition of the present branched alkyl or cycloalkyl group having 3 to 10 invention comprises (A) a silyl ester copolymer containing carbon atoms, or a Substituted or unsubstituted phe constituent units derived from a polymerizable unsaturated nyl group having 6 to 10 carbon atoms or trimeth carboxylic acid silyl ester; (B) a carboxylic acid, (C) a ylsilyloxy group. bivalent or trivalent metal compound; and (D) a dehydrating 0079 The antifouling coating composition of the present agent. invention preferably further comprises an antifouling agent Sillyl Ester Copolymer (A) (E). Copper or a copper compound (E1) is preferably contained as the antifouling agent (E). 0089 First, the silyl ester copolymer (A) will be described. The Silyl ester copolymer for use in the present 0080. It is also preferred that an organic antifouling agent invention contains constituent units derived from a poly compound (E2) excluding an organocopper compound be merizable unsaturated carboxylic acid silyl ester. contained as the antifouling agent (E). 0090 (a) Constituent Units Derived from a Polymeriz 0.081 Preferably, the antifouling coating composition of able Unsaturated Carboxylic Acid Silyl Ester the present invention further comprises an exceSS amount of 0091 As the polymerizable unsaturated carboxylic acid Zinc oxide (E) as a coating film strength increasing agent, a silyl ester, there can be mentioned, for example, a silyl ester coating film consumption regulator, a body pigment Such as of unsaturated monocarboxylic acid Such as acrylic acid or colorant, or a color pigment. The amount is up to 5000 methacrylic acid; a silyl ester of C.f3-unsaturated dicarboxy equivalents, preferably 2 to 5000 equivalents, and still lic acid Such as itaconic acid, maleicacid, fumaric acid or preferably 10 to 3000 equivalents per equivalent of carboxyl citraconic acid (dicarboxylic acid); or a silyl ester of half group of the carboxylic acid (B). ester of C.B-unsaturated dicarboxylic acid. US 2003/0207962 A1 Nov. 6, 2003
0092. The above constituent units derived from a poly identical with or different from R. Further, it is preferred merizable unsaturated carboxylic acid silyl ester are prefer that the sum of carbon atoms had by R, R and R' range ably silyl (meth)acrylate constituent units of the formula: from 5 to about 21. Among these silyl (meth)acrylates, triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acry late, di-Sec-butyl-methylsilyl (meth)acrylate, Sec-butyl-dim (I) ethylsilyl (meth)acrylate and tri-Sec-butylsilyl (meth)acry late are especially preferred from the viewpoint of easineSS CH2 in the Synthesis of silyl (meth)acrylate copolymer and from the Viewpoint of the film forming properties, Storage Stabil CRCOOSiRRR ity and easineSS in abradability control of the antifouling coating composition wherein the silyl (meth)acrylate copolymer is employed. 0093 wherein R represents a hydrogen atom or a methyl 0099 (b) Constituent Units (b) Derived from a (meth group; and R, R and R' may be identical with or different )acrylate Having a Polar Group from each other, and each thereof represents any of a 0100. In the present invention, preferably, the silyl ester hydrogen atom, an alkyl group, a cycloalkyl group, a Sub copolymer contains constituent units (b) derived from a Stituted or unsubstituted phenyl group and an alkylsilyloxy (meth)acrylate having a polar group together with the above group. This alkyl group preferably has 1 to 18 carbon atoms, constituent units (a) derived from a polymerizable unsatur Still preferably 1 to 6 carbon atoms. This cycloalkyl group ated carboxylic acid Silyl ester. preferably has 3 to 10 carbon atoms, still preferably 3 to 8 0101 The constituent units (b) derived from a (meth carbon atoms. AS the Substituent which can replace a hydro )acrylate having a polar group, although not particularly gen atom of the phenyl group, there can be mentioned, for limited as long as they are those derived from a (meth)acry example, an alkyl, an aryl or a halogen. late monomer having a polar group, are preferably constitu 0094) The silyl (meth)acrylate from which the above silyl ent units represented by the formula: (meth)acrylate constituent units can be derived can be represented by the formula: (II)
CH2 (I-a) CH2 CRCOZR6 CRICOOSiR2RR
0.095 wherein R is as defined in the above formula (I) 0102) wherein R represents a hydrogen atom or a and represents a hydrogen atom or a methyl group; and R, methyl group; and Z represents an oxygen atom or a R and R" are as defined in the above formula (I) and may group of the formula -NR", provided that: be identical with or different from each other, and each 0103) when Z is an oxygen atom, R represents a thereof represents any of a hydrogen atom, an alkyl group, Substituted or unsubstituted hydroxyalkyl group, a cycloalkyl group, a Substituted or unsubstituted phenyl hydroxycycloalkyl group, polyalkylene glycol group group and an alkylsilyloxy group. of the formula-(RO)nH (wherein R represents an alkylene group, and n is an integer of 2 to 50) or 0096 Specifically, for example, the above silyl (meth alkoxypolyalkylene glycol group of the formula )acrylate (I-a) can be a silyl (meth)acrylate of the above formula wherein R, RandR" are identical with each other, -(RO)nR' (wherein R represents an alkylene such as trimethylsilyl (meth)acrylate, triethylsilyl (meth group, R represents an alkyl group, and n is an )acrylate, tripropylsilyl (meth)acrylate, triisopropylsilyl integer of 1 to 100), and (meth)acrylate, tributylsilyl (meth)acrylate, tri-Sec-butylsi 0104 when Z is a group of the formula -NR", R' lyl (meth)acrylate or triisobutylsilyl (meth)acrylate; or a represents an alkyl group unsubstituted or Substi silyl (meth)acrylate of the above formula wherein R, R and tuted with any of a halogen, a hydroxyl group, an R" are partially or wholly different from each other, such as amino group, a Substituted amino group, an acyl di-sec-butyl-methylsilyl (meth)acrylate, sec-butyl-dimethyl group and an alkoxy group, and R represents a silyl (meth)acrylate, dimethylpropylsilyl (meth)acrylate, hydrogen atom. monomethyldipropylsilyl (meth)acrylate or methylethylpro 0105. In the above formula (II), the hydroxyalkyl group pylsilyl (meth)acrylate. preferably has 1 to 18 carbon atoms, still preferably 2 to 9 carbon atoms. The hydroxy cycloalkyl group preferably has 0097. These silyl (meth)acrylates can be used in combi 3 to 10 carbon atoms, still preferably 3 to 8 carbon atoms. nation. The alkylene group of the polyalkylene glycol group pref erably has 1 to 8 carbon atoms, still preferably 2 to 4 carbon 0098. With respect to these silyl (meth)acrylates, it is atoms. The alkylene group of the alkoxypolyalkylene glycol preferred that each of R, RandR' independently represent group preferably has 1 to 8 carbon atoms, Still preferably 2 an alkyl group having 1 to about 18 carbon atoms, Such as to 4 carbon atoms, and the alkyl group of the alkoxypoly methyl, ethyl, n-propyl, isopropyl, Sec-butyl, tert-butyl or alkylene glycol group preferably has 1 to 8 carbon atoms, isobutyl. Still preferably, R represents a branched alkyl Still preferably 2 to 4 carbon atoms. This alkyl group may group or a cycloalkyl group. Each of R and R' may be form a cyclic Structure. AS the Substituted amino group, US 2003/0207962 A1 Nov. 6, 2003 there can be mentioned a mono- or dialkylamino group 0112 These unsaturated monomers (II-a) can be used having 1 to 6 carbon atoms. AS the acyl group, there can be individually or in combination. mentioned an alkanoyl group having 1 to 6 carbon atoms. AS 0113 Among these unsaturated monomers (II-a) the alkoxy group, there can be mentioned, for example, an hydroxylated monomers are preferred. Among the hydroxy alkoxy group having 1 to 6 carbon atoms. lated monomers, the use of 2-hydroxypropyl acrylate, 2-hy 0106 The unsaturated monomer from which these unsat droxybutyl methacrylate or the like is preferred from the urated monomer constituent units (b) can be derived may be Viewpoint that an antifouling coating film of appropriate represented by the formula: elution performance can be obtained. Unsaturated Monomer Constituent Units (c) (II-a) 0114. The components of the silyl ester copolymer gen CH2 erally comprise unsaturated monomer constituent units (c) together with the above constituent units (a) and the above CRCOZR6 constituent units (b). The unsaturated monomer constituent units (c) are different from both the constituent units (a) and 0107 wherein R is as defined in the above formula the constituent units (b). (II) and represents a hydrogen atom or a methyl 0115 The unsaturated monomer (c-1) from which these group; and Z is as defined in the above formula (II) unsaturated monomer constituent units (c) can be derived and represents an oxygen atom or a group of the can Specifically be, for example, any of: formula -NR", provided that: 0116 (meth)acrylates such as methyl (meth)acry late, ethyl (meth)acrylate and octyl (meth)acrylate; 0108) when Z is an oxygen atom, R represents a Substituted or unsubstituted hydroxyalkyl group, 0117 styrenes such as styrene, vinyltoluene and hydroxycycloalkyl group, polyalkylene glycol group C.-methylstyrene, of the formula-(RO)nH (wherein R represents an 0118 vinyl esters such as vinyl acetate, vinyl ben alkylene group, and n is an integer of 2 to 50) or Zoate, Vinyl propionate and Vinyl butyrate; and alkoxypolyalkylene glycol group of the formula 0119 crotonic acid esters, itaconic acid esters, -(RO)nR' (wherein R represents an alkylene fumaric acid esters and maleic acid esters. Of these, group, R represents an alkyl group, and n is an (meth)acrylates, Styrenes and vinyl esters are pre ferred from the viewpoint that an antifouling coating integer of 1 to 100), and film of appropriate film Strength can be obtained. 0109) when Z is a group of the formula -NR7, R7 0120) These unsaturated monomers can be used individu represents an alkyl group unsubstituted or Substi ally or in combination. tuted with any of a halogen, a hydroxyl group, an 0121. In the present invention, from the viewpoint of amino group, a Substituted amino group, an acyl coating film Strength and consumability, it is preferred that group and an alkoxy group, and R represents a the silyl ester copolymer (A) contain 20 to 80% by weight, hydrogen atom. especially 30 to 70% by weight of constituent units (a) from a polymerizable unsaturated carboxylic acid silyl ester; 0 to 0110. Among these unsaturated monomers (II-a), those of 40% by weight, especially 0.1 to 20% by weight of con the formula (II-a) wherein Z represents an oxygen atom can Stituent units (b) from a (meth)acrylate having a polar group; be, for example, any of 2-hydroxyethyl acrylate, 2-hydroxy and 5 to 80% by weight, especially 10 to 60% by weight of ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydrox other unsaturated monomer constituent units (c) (provided ypropyl methacrylate, 3-chloro-2-hydroxypropyl methacry that component (a)+component (b)+component (c)=100% late, 3-phenoxy-2-hydroxypropyl acrylate, 4-hydroxybutyl by weight). acrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl meth acrylate, 6-hydroxyhexyl acrylate, 1,4-cyclohexanedimetha 0.122 Further, it is preferred that the weight average nol monoacrylate, polyethylene glycol monomethacrylate molecular weight, as measured by gel permeation chroma (n=2), polyethylene glycol monomethacrylate (n=4), poly tography (GPC), of the silyl ester copolymer (A) be 200 ethylene glycol monomethacrylate (n=5), polyethylene gly thousand or less, especially in the range of 5000 to 100 col monomethacrylate (n=8), polyethylene glycol thousand, from the Viewpoint of easineSS in the preparation monomethacrylate (n=10), polyethylene glycol of antifouling paint loaded with the Sillyl ester copolymer monomethacrylate (n=15), polypropylene glycol (A), Storage Stability of obtained antifouling paint, applica monomethacrylate (n=5), polypropylene glycol bility thereof, and consumption rate and cracking resistance monomethacrylate (n=9), polypropylene glycol of antifouling coating film. monomethacrylate (n=12), 2-methoxyethyl acrylate and methoxypolyethylene glycol monomethacrylate (n=45). Production of Silyl Ester Copolymer (A) 0123 Silyl (meth)acrylate copolymer as the silyl ester 0111. On the other hand, those of the formula (II-a) copolymer (A) can be obtained by random copolymerization wherein Z represents a group of the formula-NR7 can be, of 20 to 80% by weight of silyl (meth)acrylate (a1) repre for example, any of N-methylolacrylamide, N-methoxym sented by the above formula (I-a), 0 to 40% by weight of ethylacrylamide, N-ethoxymethylacrylamide, N,N-dimethy unsaturated monomer (b1) represented by the formula (II-a), laminopropylacrylamide, N,N-dimethylaminopropyl and 5 to 80% by weight of another unsaturated monomer methacrylamide and diacetonacrylamide. (c1) which is copolymerizable with the above monomers US 2003/0207962 A1 Nov. 6, 2003
(a1) and (b1) (provided that component (a1)+component 0136 silyl (meth)acrylate constituent units (e) rep (b1)+component (c1)=100% by weight) in the presence of a resented by the formula: radical polymerization initiator according to various meth ods, Such as Solution polymerization, bulk polymerization, emulsion polymerization and Suspension polymerization. (I-b) 0.124 Conventional azo compounds, peroxides and the like can widely be used as the radical polymerization CH2 initiator. Examples of the azo compounds include 2,2'- CR 10COOSiR1R15R 16 azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile). 0.125 Examples of the peroxides include benzoyl perox ide, tert-butyl peroxyacetate, tert-butyl peroxyoctate, 0137) wherein R" represents a hydrogen atom or a cumene hydroperoxide, tert-butyl peroxide, tert-butyl per methyl group; each of R'' and R' independently oxybenzoate, tert-butyl peroxyisopropyl carbonate, tert-bu represents a branched alkyl or cycloalkyl group tyl hydroperoxide and perSulfates (potassium and ammo having 3 to 10 carbon atoms; and R' represents a nium salts). linear alkyl group having 1 to 10 carbon atoms, a 0.126 When the above polymer is used in an antifouling branched alkyl or cycloalkyl group having 3 to 10 paint, the Solution polymerization in which polymerization carbon atoms, or a Substituted or unsubstituted phe is carried out in an organic Solvent, or the bulk polymeriza nyl group having 6 to 10 carbon atoms or trimeth tion is preferred among the above various polymerization ylsilyloxy group. methods. The organic Solvent used in the Solution polymer ization method can be, for example, any of: 0138. The constituent units (d), (e) and (f) which consti tute this silyl (meth)acrylate copolymer (A-1) will be 0127 aromatic hydrocarbons such as xylene and described in Sequence below. toluene, 0128 aliphatic hydrocarbons such as hexane and Silyl (meth)acrylate Constituent Units (d) heptane, 013:9) The silyl (meth)acrylate constituent units (d) are 0.129 esters such as ethyl acetate and butyl acetate; represented by the formula: 0.130 alcohols such as isopropyl alcohol and butyl alcohol, (I-a) 0131) etherS Such as dioxane and diethyl ether, and 0132 ketones such as methyl ethyl ketone and CH2 methyl isobutyl ketone. These solvents can be used CR 10COOSiR 11R12R 13 individually or in combination. Silyl Ester Copolymer (A-1) 0133. In the present invention, as the silyl ester copoly 0140) wherein R' represents a hydrogen atom or a mer (A), there can be employed a silyl (meth)acrylate methyl group; and each of R'' and R' independently rep copolymer containing: resents a linear alkyl group having 1 to 10, preferably 1 to 0134 silyl (meth)acrylate constituent units (d) rep 8, and still preferably 1 to 6 carbon atoms, or a substituted resented by the formula: or unsubstituted phenyl group or trimethylsilyloxy group. AS the linear alkyl group, there can be mentioned, for example, any of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, (I-a) n-heptyl, n-octyl, n-nonyl and n-decyl groups.
CH2 0.141. As the substituent which can replace a hydrogen atom of the phenyl group, there can be mentioned, for CR 10COOSiR11R12R 13 example, an alkyl, an aryl or a halogen. 0142) R' represents a cyclic or acyclic, branched or unbranched alkyl group having 1 to 18 carbon atoms, 0135) wherein R' represents a hydrogen atom or a preferably 1 to 12 carbon atoms, and still preferably 1 to 9 methyl group; each of R' land R' independently carbon atoms, a Substituted or unsubstituted phenyl group represents a linear alkyl group having 1 to 10 carbon having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, atoms, or a Substituted or unsubstituted phenyl group or a trimethylsilyloxy group of the formula (CH)SiO-. or trimethylsilyloxy group; and R' represents a 0143. This alkyl group can be any of the above listed cyclic or acyclic, branched or unbranched alkyl linear alkyl groups, and further can be: group having 1 to 18 carbon atoms, or a Substituted or unsubstituted phenyl group having 6 to 10 carbon 0144) a branched alkyl group Such as isopropyl, atoms or trimethylsilyloxy group, and isobutyl, Sec-butyl, tert-butyl or neopentyl, US 2003/0207962 A1 Nov. 6, 2003
0145 an alicyclic alkyl group having an alicyclic 0172 methylethyl-n-propylsilyl (meth)acrylate, Structure (e.g., cyclohexane ring or norbornane ring), Such as cyclohexyl or ethylidenenorbornyl, 0173 ethylidenenorbornyl-dimethylsilyl (meth) acrylate, and 0146 or the like. 0147 Of these, R', R'' and R', although may be 0.174 trimethylsilyloxy-dimethylsilyl (meth) identical with or different from each other, preferably each acrylate represent methyl, ethyl, n-propyl, n-butyl, n-hexyl or trim (CH=C(CH)COOSi(CH)(OSi(CH)) or ethylsilyloxy, and Still preferably each represent methyl, CH=CHCOOSi(CH)(OSi(CH))). n-propyl, n-butyl or n-hexyl. 0175. In the present invention, these silyl (meth)acrylates 0148 The silyl (meth)acrylate (d1) from which the above (I-a-1) can be used individually or in combination. silyl (meth)acrylate constituent units (d) can be derived can be represented by the formula: Silyl (meth)acrylate Constituent Units (e) 0176) The silyl (meth)acrylate constituent units (e) are (I-a-1) CH2 represented by the formula: CR 10COOSiR 11R12R13 (I-b)
01491 wherein R' to R' are as defined in the above CH2 formula (I-a). CR 10COOSiR1R15R 16 0150 Specifically, the silyl (meth)acrylate of the formula (I-a-1) can be, for example, any of (015.1) aliphatic silyl (meth)acrylates wherein Ril, R and R' are identical with each other, such as: 0177 wherein R' represents a hydrogen atom or a 0152) trimethylsilyl (meth)acrylate, methyl group; and each of R'' and R' independently represents a branched alkyl group having 3 to 10, preferably 0153 triethylsilyl (meth)acrylate, 3 to 8 carbon atoms, or a cycloalkyl group having 3 to 10, 0154) tri-n-propylsilyl (meth)acrylate, preferably 3 to 9 carbon atoms. 0.155) tri-n-butylsilyl (meth)acrylate, 0.178 This branched alkyl group is as defined in the above formula (I), and can be, for example, any of isopropyl, 0156) tri-n-pentylsilyl (meth)acrylate, isobutyl, Sec-butyl, tert-butyl and neopentyl. O157) tri-n-hexylsilyl (meth)acrylate, 0179 The above cycloalkyl group can be, for example, 0158] tri-n-heptylsilyl (meth)acrylate, cyclohexyl or ethylidenenorbornyl. 0159) tri-n-octylsilyl (meth)acrylate, 0180) R' represents a linear alkyl group having 1 to 10, 0.160) tri-n-nonylsilyl (meth)acrylate, and preferably 1 to 8, and still preferably 1 to 6 carbon atoms; tri-n-decylsilyl (meth)acrylate, a branched alkyl or cycloalkyl group having 3 to 10, 0161) preferably 3 to 9 carbon atoms; a substituted or unsubsti 0162 aromatic or siloxane silyl (meth)acrylates tuted phenyl group having 6 to 10, preferably 6 to 8 carbon wherein R', R'' and R' are identical with each atoms, or a trimethylsilyloxy group. other, Such as: 0181. As the linear alkyl group, branched alkyl or 0163) triphenylsilyl (meth)acrylate, and cycloalkyl group and phenyl group represented by R', there 0164) tris(trimethylsilyloxy)silyl (meth)acrylate, can be mentioned, for example, the same Specific groups as and listed above. (0165) aliphatic silyl (meth)acrylates wherein R', 0182) Of these, when R', R' and R', although may be R" and R' are partially or wholly different from identical with or different from each other, are identical with each other, Such as: each other, it is preferred that isopropyl, Sec-butyl or isobu dimethyl-n-propylsilyl (meth)acrylate, tyl be represented thereby. It is especially preferred that 0166) isopropyl or Sec-butyl be represented thereby. 0167) isopropyldimethylsilyl (meth)acrylate, 0183) When R', R' and R' are partially or wholly 0168) di-n-butyl-isobutylsilyl (meth)acrylate, different from each other, it is preferred that R'' and R', 0169 n-hexyl-dimethylsilyl (meth)acrylate, although may be identical with or different from each other, each represent isopropyl, isobutyl, Sec-butyl or tert-butyl. It 0.170) Sec-butyl-dimethylsilyl (meth)acrylate, is preferred that R' represent a group selected from among 0171 monomethyldi-n-propylsilyl (meth)acry methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and trim late, ethylsilyloxy. US 2003/0207962 A1 Nov. 6, 2003
0184 The silyl (meth)acrylate (e1) from which the above 0210 trimethylsilyloxy-dimethylsilyl (meth) silyl (meth)acrylate constituent units (e) can be derived can acrylate, be represented by the formula: 0211 bis(trimethylsilyloxy)-methylsilyl (meth) acrylate, and (I-b-1) CH2 0212 tris(trimethylsilyloxy)silyl (meth)acrylate, CR 10COOSiR 14R 15R 16 0213 with at least one silyl (meth)acrylate (I-b-1) Selected from among: 0214) triisopropylsilyl (meth)acrylate, 0185 wherein R, R', R' and Rare as defined in the above formula (I-b). 0215 triisobutylsilyl (meth)acrylate, 0186 The silyl (meth)acrylate of the formula (I-b-1) can 0216 tri-sec-butylsilyl (meth)acrylate, Specifically be, for example, any of 0217 di-sec-butyl-methylsilyl (meth)acrylate, (0187 silyl (meth)acrylates wherein R', R' and Rare identical with each other, Such as: 0218 diisopropyl-trimethylsilyloxysilyl (meth) acrylate, and 0188) triisopropylsilyl (meth)acrylate, 0219 di-sec-butyl-trimethylsilyloxysilyl (meth) 0189) triisobutylsilyl (meth)acrylate, and acrylate. 0.190) tri-sec-butylsilyl (meth)acrylate, and 0220. It is still preferred to employ a combination of 0191) silyl (meth)acrylates wherein R', Rand R' tri-n-butylsilyl (meth)acrylate as the silyl (meth)acrylate are partially or wholly different from each other, (I-a-1) with triisopropylsilyl (meth)acrylate as the silyl Such as: (meth)acrylate (I-b-1). 0192 diisopropyl-cyclohexylsilyl (meth)acrylate, 0221 (Unsaturated monomer constituent units (f)) 0193 diisopropyl-phenylsilyl (meth)acrylate, 0222 The unsaturated monomer constituent units (f), 0194 diisopropyl-trimethylsiloxysilyl (meth) together with the above constituent units (d) and constituent acrylate, units (e), constitute the Silyl (meth)acrylate copolymer of the present invention. These unsaturated monomer constituent 0195 di-sec-butyl-methylsilyl (meth)acrylate, units (f) are different from both the constituent units (d) and 0196) di-sec-butyl-ethylsilyl (meth)acrylate, constituent units (e), AS the unsaturated monomer (f1) from which the unsaturated monomer constituent units (f) can be 0197) di-sec-butyl-trimethylsilyloxysilyl (meth) derived, there can be mentioned the (meth)acrylate having a acrylate, and polar group (b), represented by the above formula (II-a), and 0198 isopropyl-sec-butyl-methylsilyl (meth) the unsaturated monomer (c-1) from which the unsaturated acrylate. monomer constituent units (c) can be derived. 0223) The unsaturated monomer (f1) can specifically be, 0199. In the present invention, these silyl (meth)acrylates for example, any of: (I-b-1) can be used individually or in combination. 0200 Among the above silyl (meth)acrylates, from the 0224 hydrophobic (meth)acrylates such as methyl Viewpoint of easiness in the Synthesis of silyl (meth)acrylate (meth)acrylate, ethyl (meth)acrylate, n-, iso- or tert copolymer and from the viewpoint of the film forming butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate properties, Storage Stability and easineSS in abradability and cyclohexyl (meth)acrylate; control of the antifouling coating composition loaded with 0225 hydrophilic (meth)acrylates such as 2-hy the silyl (meth)acrylate copolymer, it is preferred to employ droxyethyl (meth)acrylate, 2-hydroxypropyl (meth) a combination of: acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxy butyl (meth)acrylate, 2-methoxyethyl (meth)acry 0201 at least one silyl (meth)acrylate (I-a-1) late, alkoxypolyethylene glycol mono(meth)acrylate Selected from among: and alkoxypolypropylene glycol mono(meth)acry 0202) trimethylsilyl (meth)acrylate, late; 0203) triethylsilyl (meth)acrylate, 0226 styrenes such as styrene, vinyltoluene and C.-methylstyrene, 0204) tri-n-propylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, 0227 vinyl esters such as vinyl acetate, vinyl ben 0205) Zoate, Vinyl propionate and Vinyl butyrate; and 0206 n-hexyl-dimethylsilyl (meth)acrylate, 0228 carboxylic acid esters such as itaconic acid 0207 n-octyl-dimethylsilyl (meth)acrylate, esters and maleic acid esters. Of these, (meth)acry isopropyl-dimethylsilyl (meth)acrylate, lates, Styrenes and carboxylic acid vinyl esters are 0208) preferred from the Viewpoint that an antifouling 0209 ethylidenenorbornyl-dimethylsilyl (meth) coating film of appropriate film Strength can be acrylate, obtained. US 2003/0207962 A1 Nov. 6, 2003
0229. In particular, when hydrophilic (meth)acrylates are 0239 esters such as ethyl acetate and butyl acetate; employed, the consumability of coating film can be increased. For this purpose, also, use can be made of a 0240 alcohols such as isopropyl alcohol and butyl hydrophilic comonomer Such as an acrylamide derivative. alcohol; 0230. These unsaturated monomers (f1) can be used 0241 ethers such as dioxane and diethyl ether; and individually or in combination. 0242 ketones such as methyl ethyl ketone and 0231. From the viewpoint of prevention of coating film methyl isobutyl ketone. These solvents can be used cracking, resistance to coating film peeling, coating film individually or in combination. Strength and consumability, it is preferred that the Silyl (meth)acrylate copolymer of the present invention contain 0243 Carboxylic Acid (B), Bivalent or Trivalent Metal 0.5 to 50% by weight, especially 0.5 to 25% by weight of Compound (C) and Formed Carboxylic Acid Excess-Metal silyl (meth)acrylate constituent units (d); 10 to 70% by Salt weight, especially 30 to 65% by weight of silyl (meth)acry late constituent units (e); and 20 to 70% by weight, espe 0244)
0255 Sandarach resin containing Sandaracopimalic 0266)
calculated by determining the amount of metal contained in metal Salt in the paint. In particular, with respect to, the carboxylic acid exceSS-metal Salt through, for example, for example, a System (System consisting of carboxy a chelatometric titration analysis of Solvent Soluble contents. lic acid (B) and bivalent or trivalent metal compound 0277 Hitherto, with respect to, for example, a compound (C)) wherein an isononanoic acid exceSS-metal Salt is constituted of a monocarboxylic acid (RCOOH) and a formed, the hygroscopic property is conspicuous, So bivalent metal (M), an equal-equivalent reaction product that a stable coating composition can be obtained. represented by the formula (RCOO)M has been proposed 0284. In the present invention, depending on the condi as a carboxylic acid metal Salt for use in antifouling paints. tions for preparation of the antifouling coating composition, 0278 In contrast, when in an antifouling coating com various carboxylic acid derivatives can be used in place of position the carboxylic acid (B) and the bivalent or trivalent the above carboxylic acid (B) so as to form the carboxylic metal compound (C) are contained in Such a proportion that acid exceSS-metal Salt through reaction between the car the carboxylic acid exceSS-metal Salt is formed, there can be boxylic acid derivatives and the bivalent or trivalent metal obtained a paint having the following excellent characteris compound (C) in the antifouling coating composition or the tics. coating film. 0279 (1) The carboxylic acid excess-metal salt 0285) In that instance, the modes of reaction between the which is a compound of lower viscosity than that of carboxylic acid or derivatives thereof and the bivalent or the conventional equal-equivalent reaction product trivalent metal compound (C) in the antifouling coating can be obtained, So that a paint of low Viscosity can composition, as described in the applicant's prior applica be prepared with the result that a paint of lowered tion Japanese Patent Application 2000-292.907 (filed on Sep. Solvent content can be obtained. 25, 2000), columns 0106 to 0111, can include: 0280 (2) A large amount of unreacted carboxylic 0286 (i) direct reaction between a carboxylic acid or acid is present in the conventional equal-equivalent derivative thereof and the above metal, reaction product (carboxylic acid metal Salt), So that there has been a tendency toward deteriorations of 0287 (ii) reaction between a carboxylic acid or Storage Stability and antifouling properties attributed derivative thereof and an oxide, hydroxide or car to the reaction with active components of the paint. bonate of the above metal, By contrast, when the organic carboxylic acid (B) 0288 (iii) reaction between an alkali metal salt of and the bivalent or trivalent metal compound (C) are carboxylic acid and a water-soluble salt of the above contained in Such a proportion that the carboxylic metal, etc. acid exceSS-metal Salt is formed according to the present invention, the amount of unreacted carboxy 0289. In the present invention, the reaction (ii) between a lic acid is extremely Small, or any unreacted car carboxylic acid or derivative thereof and an oxide, hydrox boxylic acid is Substantially not present. Thus, the ide or carbonate of metal is preferred from the viewpoint of above disadvantage can be avoided, and neither easineSS in controlling of equivalent ratio, high reactivity deterioration of Storage Stability nor deterioration of and Stable reaction. antifouling properties would be invited. 0290 The above carboxylic acids can be used, and as the 0281. In particular, when not only zinc oxide (zinc white) carboxylic acid derivatives, there can be mentioned, for added for the purpose of formation of carboxylic acid example, alkali metal Salts, quaternary ammonium Salts, exceSS-metal Salt but also Zinc oxide (Zinc white) added for quaternary phosphonium Salts and esters. Examples of the the purpose of increase of coating film Strength, regulation alkali metal Salts include Sodium and potassium Salts. The of coating film consumption and coloring, etc. is present in quaternary ammonium Salts may be Substituted with alkyl a paint, water would be formed by reaction between unre groups having 1 to 15, preferably 1 to 10 hydrogen atoms. acted carboxylic acid and Zinc oxide. This water or the like, The quaternary phosphonium Salts may be Substituted with for example, may accelerate the hydrolysis of component alkyl groups having 1 to 15, preferably 1 to 10 hydrogen (A), thereby deteriorating the storage stability of paint. atoms. AS the esters, there can be mentioned those of neutral fat or oil structure. 0282. However, the antifouling coating composition of the present invention is loaded with not only the carboxylic 0291. As the water-soluble salt of metal, there can be acid (B) and the above proportion of metal compound (C) mentioned, for example, a chloride, a bromide, a nitrate, a but also a dehydrating agent (D). Consequently, the reaction Sulfate, a phosphate, a carbonate or a bicarbonate. between the organic carboxylic acid (B) and the bivalent or 0292. These antifouling coating compositions may con trivalent metal compound (C) is effectively advanced to tain the above Solvents according to necessity. thereby result in formation of the carboxylic acid exceSS metal Salt. Thus, any unreacted carboxylic acid is Substan Dehydrating Agent (D) tially not present, So that after the consumption of carboxylic 0293 The dehydrating agent (D) functions, for example, acid (B) by reaction with the component (C), there would be to remove water formed by reaction between the carboxylic no reaction with remaining Zinc oxide. Therefore, a paint of acid (B) and the bivalent or trivalent metal compound (C), excellent Storage Stability can be obtained. especially Zinc oxide, as mentioned above, to accelerate the 0283 (3) The formed carboxylic acid excess-metal formation of carboxylic acid exceSS-metal Salt and to pre Salt per Se is hygroscopic, thereby contributing to vent the hydrolysis of silyl ester copolymer (A), thereby enhancement of the Storage Stability of paint owing contributing to the Storage Stability of antifouling coating to the dehydrating action of carboxylic acid exceSS composition. US 2003/0207962 A1 Nov. 6, 2003
0294. A wide variety of known dehydrating agents can be 0306 Still further, in the antifouling coating composition, used as the dehydrating agent (D). The antifouling coating it is preferred that per 100 parts by weight of silyl ester composition of the present invention is loaded with an copolymer (A) (Solid contents): inorganic or organic dehydrating agent, preferably an inor ganic dehydrating agent. By virtue of the loading with the 0307 the carboxylic acid (B) be contained in an dehydrating agent, the antifouling coating composition of amount of 0.04 to 2000 parts by weight, especially the present invention is excellent in Storage Stability. 10 to 600 parts by weight; 0295 Specifically, the dehydrating agent can be, for 0308 the bivalent or trivalent metal compound (C) example, any of anhydrous gypsum (CaSO), Synthetic be contained in an amount of 3.0 to 2400 parts by Zeolite adsorbents (trade name: Molecular Sieve, etc.), weight, especially 8 to 1200 parts by weight; and orthoesterS Such as methyl orthoformate and methyl orthoac 0309 the dehydrating agent (D) be contained in an etate, orthoboric esters, Silicates and isocyanates (trade amount of 0.02 to 100 parts by weight, especially 0.2 name: Additive T1). In particular, anhydrous gypsum and to 50 parts by weight. Molecular Sieve are preferably used as the inorganic dehy drating agent. Such inorganic dehydrating agents can be 0310. When the components (A), (B), (C) and (D) are used individually or in combination. contained in the antifouling coating composition in these amounts, there can be realized Such a tendency that not only 0296. It is preferred that this dehydrating agent, espe is the Storage Stability of paint excellent but also the anti cially the inorganic dehydrating agent be contained in an fouling coating film exhibits less cracking occurrence, amount of 0.15 to 50 equivalents, especially 0.2 to 30 excellent adherence So as to ensure leSS peeling occurrence equivalents, per equivalent of carboxyl group of the car and desirably controlled hydrolysis rate So as to be excellent boxylic acid (B) contained in the antifouling coating com in antifouling performance, in particular, antifouling prop position. erties in Stationary environment or highly fouling environ 0297. It is generally preferred that this dehydrating agent, ment and long-term antifouling properties with a good especially the inorganic dehydrating agent be added in an balance therebetween. amount of 0.02 to 100 parts by weight, especially 0.2 to 50 parts by weight, per 100 parts by weight of silyl ester Various Additives copolymer (A). 0311. The antifouling coating composition (P) of the 0298. Further, it is generally preferred that such inorganic present invention, comprising the above silyl ester copoly dehydrating agents, in total, be contained in an amount of mer (A), carboxylic acid (B), bivalent or trivalent metal 0.01 to 20% by weight, especially 0.1 to 8% by weight, compound (C) and dehydrating agent (D) as essential com based on the antifouling coating composition. ponents, may further contain various additives as other components. 0299 When the dehydrating agent, especially the inor ganic dehydrating agent is contained in the antifouling 0312. As the various additives, there can be mentioned, coating composition in the above amount, there is a ten for example, an antifouling agent (E), Zinc oxide (Zinc dency toward Striking enhancement of the Storage Stability white) (F), an antisagging/antisetting agent, an elution accel of the antifouling coating composition. erating component (G), a plasticizer Such as chlorinated paraffin, various pigments Such as a color pigment and a body pigment, various resins Such as an acrylic resin and a Antifouling Coating Composition polyalkyl vinyl ether (vinyl ether (co)polymer), and other 0300. The antifouling coating composition of the present various additives Such as a defoamer, an antiflooding agent invention comprises the above silyl ester copolymer (A) and a leveling agent. (including copolymer (A-1)), carboxylic acid (B), bivalent or trivalent metal compound (C) and dehydrating agent (D). Antifouling agent (E) 0301 In the antifouling coating composition (containing 0313 Although the antifouling agent (E) may be inor ganic or organic and a wide variety of known antifouling solvent and various additives described later) of the present agents can be used, it is preferred in the present invention to invention, it is preferred that the silyl ester copolymer (A) be employ copper and/or a copper compound (E1), or an contained in an amount of 2 to 60% by weight, especially 5 organic antifouling agent Such as a metal pyrithione (E2) to 40% by weight. (organic antifouling agents excluding copper compounds, 0302 Further, in the antifouling coating composition, it is the same applies hereinafter). preferred that: 0314. The copper and/or copper compound (E1) to be 0303 the carboxylic acid (B) be contained in an added to the antifouling coating composition of the present amount of 0.1 to 60% by weight, especially 0.5 to invention will now be described. The molecular weight of 40% by weight; the copper and/or copper compound is generally in the range of 63.5 to 2000, preferably 63.5 to 1000. 0304 the bivalent or trivalent metal compound (C) be contained in an amount of 0.1 to 60% by weight, 0315 Both organic and inorganic copper compounds can especially 0.5 to 40% by weight; and be used as the copper compound (E1) among the compo nents (E1). Examples of the inorganic copper compounds 0305 the dehydrating agent (D) be contained in an include cuprous oxide, copper thiocyanate (cuprous thiocy amount of 0.01 to 30% by weight, especially 0.1 to anate or copper rhodanate), basic copper Sulfate, copper 10% by weight. chloride and copper oxide. US 2003/0207962 A1 Nov. 6, 2003
0316 Examples of the organic copper compounds contained together with the pyrithione compounds or in include basic copper acetate, Oxine copper, copper non place of the pyrithione compounds. Various known antifoul ylphenolsulfonate, products of reaction between a resin acid ing agents can be used as the other organic antifouling Such as rosin and copper or a copper compound, copper agents. bis(ethylenediamine)-bis(dodecylbenzenesulfonate), copper 0326 Examples of the other organic antifouling agents naphthenate, copper bis(pentachlorophenolate) and copper include tetramethylthiuram disulfide, carbamate compounds pyrithione. Among these, inorganic cuprous oxide, products (e.g., Zinc dimethyldithiocarbamate and manganese 2-eth of reaction between a resin acid Such as rosin and copper or ylenebisdithiocarbamate), 2,4,5,6-tetrachloroisophthaloni a copper compound, and copper thiocyanate (copper rhodan trile, N,N-dimethyldichlorophenylurea, 2-methylthio-4-tert ate) are preferably used. butylamino-6-cyclopropylamino-S-triazine, 4,5-dichloro-2- 0317. When carboxylic acid copper salts, such as copper n-octyl-4-isothiazolin-3-one, 2,4,6- acetate, copper naphthenate and products of reaction trichlorophenylmaleimide, pyridine-triphenylborane and between a resin acid Such as rosin and copper or a copper amine-triphenylborane. compound, are used as the antifouling agent, the employed 0327 In the present invention, these organic antifouling carboxylic acid copper Salts may be in the form of a Salt agents can be used individually or in combination, together consisting of a carboxylic acid and copper used in equal with pyrithione compounds (metal pyrithiones) Such as equivalents in place of the above carboxylic acid exceSS copper pyrithione. For example, copper pyrithione can be metal salt formed by reaction between the carboxylic acid used in combination with 4,5-dichloro-2-n-octyl-4-isothia (B) and the metal compound (C). Zolin-3-one. 0318. These copper compounds, in place of copper or 0328. The total content of various antifouling agents, together with copper, can be used individually or in com Such as copper and/or copper compounds (E1) and bination. pyrithione compounds, in the antifouling coating composi 03.19. In the antifouling coating composition of the tion, although it depends on the types of coating film present invention, it is preferred that these copper and/or forming copolymer and antifouling agent used in the prepa copper compounds (E1) including those added for the for ration of antifouling coating composition and the type of, for mation of carboxylic acid exceSS-copper Salt, in total, be example, marine vessel to be coated with the antifouling generally contained in an amount of 1 to 70% by weight, coating composition (with, respect to marine vessel, whether especially 3 to 65% by weight. OverSeas Voyage, or coastwise Service, or various Sea water 0320 Per 100 parts by weight of silyl ester copolymer areas, whether wooden or steel made, etc.) and cannot be (A) contained in the antifouling coating composition, it is unconditionally determined, is preferably in the range of 10 preferred that these copper and/or copper compounds (E1), to 1400 parts by weight, still preferably 20 to 1300 parts by in total, be generally contained in an amount of 3 to 1400 weight, per 100 parts by weight of the above silyl ester parts by weight, especially 10 to 1300 parts by weight. copolymer (A). 0329. When the total content of antifouling agents is less 0321) When the copper and/or copper compounds are than 10 parts by weight, poor antifouling properties may contained in the antifouling coating composition in the result. On the other hand, when the total content of anti amount falling within the above ranges, an antifouling fouling agents exceeds 140 parts by weight, further enhance coating film having excellent antifouling properties can be ment of antifouling properties cannot be anticipated, and formed. poor cracking resistance may result. 0322. In the present invention, as the antifouling agent, 0330 For example, when copper pyrithione is used in an organic antifouling agent (E2) (excluding organocopper combination with cuprous oxide CuO) as the antifouling compounds Such as copper pyrithione included in the com agent in the antifouling coating composition, it is preferred ponent (E1)) can be used together with the copper and/or that in the antifouling coating composition the copper copper compound (E1) or in place of the copper and/or pyrithione be contained in an amount of 2 to 200 parts by copper compound (E1). weight per 100 parts by weight of silyl ester copolymer (A), 0323 AS the organic antifouling agent, there can be while the cuprous oxide be contained generally in an amount employed, for example, metal pyrithiones. Examples of the of about 10 to 1300 parts by weight per 100 parts by weight metal pyrithiones include Sodium, magnesium, calcium, of silyl ester copolymer (A). barium, aluminum, copper, Zinc, iron and lead pyrithiones. Of these metal pyrithiones, copper pyrithione is preferred. Zinc Oxide (Zinc White) (F) 0331. The antifouling coating composition of the present 0324. In the antifouling coating composition of the invention may be further loaded with zinc oxide (zinc white) present invention, it is preferred that these pyrithione com (F) for the purpose of fulfilling functions other than those of pounds, in total, be generally contained in an amount of 0.1 the above bivalent or trivalent metal compound (C), for to 15% by weight, especially 0.5 to 10% by weight. Per 100 example, for allowing it to function as an enhancer of parts by weight of silyl ester copolymer (A) contained in the coating film Strength, a regulator of coating film consump antifouling coating composition, it is preferred that these tion, a colorant, a body pigment, etc. With respect to the pyrithione compounds, in total, be generally contained in an antifouling coating composition loaded with Zinc oxide, the amount of 0.3 to 300 parts by weight, especially 2 to 200 obtained coating film exhibits enhanced Strength, and the parts by weight. abradability of coating film can be effectively controlled. 0325 In the present invention, the following organic 0332. It is preferred that zinc oxide (F) be contained in antifouling agents (other organic antifouling agents) may be the antifouling coating composition of the present invention US 2003/0207962 A1 Nov. 6, 2003 in an exceSS amount of up to 5000 equivalents, especially 2 0342. When the content of elution accelerating compo to 5000 equivalents, and still especially 10 to 3000 equiva nents in the antifouling coating composition falls within lents per equivalent of carboxyl group of the carboxylic acid these ranges, the antifouling performance and coating film (B) for the purpose of fulfilling functions other than those of consumability tend to be enhanced. the above bivalent or trivalent metal compound (C) and for allowing it to function as an enhancer of coating film Vinyl Ether (co)polymer (H) Strength, a regulator of coating film consumption, a body 0343 The vinyl ether (co)polymer comprises vinyl ether pigment or color pigment Such as a colorant, etc. constituent units, contributes to enhancement of the cracking resistance, peeling resistance and elution Velocity Stability of 0333. From the viewpoint of regulation of coating film obtained coating film, and further functions as a coating film consumption and regulation of coating film hardness, it is forming component. generally preferred that the Zinc oxide be contained in the antifouling coating composition in a total amount, including 0344) The vinyl ether (co)polymer can be, for example, that added as the bivalent or trivalent metal compound (C), any of polyvinyl methyl ether, polyvinyl ethyl ether, poly of 0.1 to 35% by weight, especially 0.5 to 25% by weight. Vinyl isopropyl ether and polyvinyl isobutyl ether. Also, it is generally preferred that the Zinc oxide be con 0345. It is generally preferred that the vinyl ether tained in an amount of 1.5 to 1200 parts by weight, espe (co)polymer (H) be contained in a total amount of 0.1 to 10 cially 4 to 600 parts by weight per 100 parts by weight of parts by weight, especially 0.2 to 5 parts by weight, per 100 silyl ester copolymer (A) in the antifouling coating compo parts by weight of antifouling coating composition. Per 100 Sition. parts by weight of silyl ester copolymer (A) contained in the antifouling coating composition, it is generally preferred Elution Accelerating Component (G) that the vinyl ether (co)polymer be contained in an amount 0334. The antifouling coating composition of the present of 0.3 to 60 parts by weight, especially 0. 6 to 40 parts by invention may contain an elution accelerating component weight. (G). 0346) When the content of vinyl ether (co)polymer in the 0335 Provided, however, that the elution accelerating antifouling coating composition falls within these ranges, component (G) excludes the above resin acids, other organic the cracking resistance, peeling resistance and elution Veloc acids (e.g., isononanoic acid, versatic acid and naphthenic ity Stability of obtained coating film tend to be enhanced. acid) and the like (the same applies hereinafter). 0347 Moreover, various polymers having a hydrophilic group can be used in place of the vinyl ether (co)polymer or 0336 The elution accelerating component (G) can be, for together with the vinyl ether (co)polymer. The polymers example, any of rosin derivatives and carboxylic acid metal having a hydrophilic group can be, for example, various salts other than the above carboxylic acids (B). (alkoxy)polyalkylene glycol mono(meth)acrylate (co)poly 0337 Examples of the rosin derivatives include polymer CS Such S (methoxy)polyethylene glycol ized rosin, maleic roSin, aldehyde-modified rosin, polyoxy mono(meth)acrylate (co)polymer. The same effect as alkylene esters of rosin, reduced rosin (rosin alcohol), metal exerted by the vinyl ether (co)polymer can be realized by the Salts of rosin (e.g.,copper, Zinc, magnesium and potassium use of these polymers. Salts of rosin) and rosin amine. These rosin derivatives can be used individually or in combination. Plasticizer (I) 0348 AS the plasticizer, there can be employed plasti 0338 Examples of the carboxylic acid metal salts include cizers customarily used in paints, Such as orthophosphoric copper (Cu), Zinc (Zn), magnesium (Mg) and calcium (Ca) acid esters, chlorinated paraffin, phthalic acid esters and Salts. AS the carboxylic acid metal Salts, use can be made of adipic acid esters. These plasticizers can be used individu those which are not the above carboxylic acid exceSS-metal ally or in combination. Salts and which consist of a carboxylic acid and a metal, the equivalent ratio of metal to carboxylic acid being 1 or less. 0349 When these plasticizers are used, they are added to the antifouling coating composition in an amount of, for 0339 Among these elution accelerating components, example, 0.1 to 10% by weight based on the antifouling rosin derivatives are preferred. These elution accelerating coating composition. components can be used individually or in combination. 0350. These plasticizers contribute to enhancement of the 0340. It is preferred that these elution accelerating com cracking resistance of coating film (also referred to as ponents be contained in an amount of 0.1 to 30 parts by “antifouling coating film” herein) formed from the resultant weight, especially 0.1 to 20 parts by weight, and Still antifouling coating composition. Among the above plasti especially 0.5 to 15 parts by weight, per 100 parts by weight cizers, chlorinated paraffin and orthophosphoric acid esters, of antifouling coating composition. The content of elution such as tricresyl phosphate (TCP), are preferred. accelerating components is preferred to fall within these 0351. The chlorinated paraffin may be linear or branched, ranges from the Viewpoint of the antifouling performance and may be liquid or Solid (powdery) at room temperature. and water resistance of coating film. AS the chlorinated paraffin, there can be mentioned, for 0341 Per 100 parts by weight of silyl ester copolymer example, “Toyoparax 150' and “Toyoparax A-70' produced (A) contained in the antifouling coating composition, it is by ToSoh Corporation. In the present invention, two or more generally preferred that the elution accelerating components, chlorinated paraffins which are different from each other in, in total, be contained in an amount of 0.3 to 600 parts by for example, the chlorine content and the number of carbon weight, especially 2 to 300 parts by weight. atoms can be used in appropriate combination. US 2003/0207962 A1 Nov. 6, 2003
0352. When the above chlorinated paraffin is used as the antifouling coating composition. The above Solvent used in plasticizer (I), it is generally preferred that the chlorinated the preparation of silyl ester copolymer (A) may be included paraffin be contained in an amount of 0.05 to 20 parts by in the Solvent contained in the antifouling coating compo weight, especially 0.1 to 15 parts by weight, per 100 parts by Sition of the present invention. weight of antifouling coating composition. Per 100 parts by weight of silyl ester copolymer (A) (Solid contents) con Various Resins tained in the antifouling coating composition, it is preferred 0360 AS additional various resins, there can be men that the chlorinated paraffin be contained in an amount of 1 tioned acrylic resins, Such as an acrylic ester (co)polymer, a to 50 parts by weight, especially 2 to 40 parts by weight. methacrylic ester (co)polymer and a 2-hydroxyethyl acrylate (co)polymer. Further, the antifouling coating composition of When the amount of chlorinated paraffin falls within these the present invention may be loaded with silyl ester ranges, the effect of Suppressing coating film cracking, (co)polymers described in, for example, Japanese Patent coating film strength and damaging (impact) resistance Laid-open Publication Nos. 4(1992)-264170, 4(1992)- would be enhanced. 264169, 4(1992)-264168, 2(1990)-196869 and 63(1988)- 0353 When an orthophosphoric ester is used as the 215780, Published Japanese Translation of PCT Patent plasticizer (I), it is generally preferred that the orthophos Applications from Other States, No. 60(1985)-500452 phoric ester be contained in an amount of 0.05 to 20 parts by (Japanese Patent Publication No. 5(1993)-32433) and Japa weight, especially 0.1 to 15 parts by weight, per 100 parts by nese Patent Laid-open Publication No. 7(1995)-18216. weight of antifouling coating composition. 0361 (Production of antifouling coating composition) 0354 Per 100 parts by weight of silyl ester copolymer 0362. The antifouling coating composition of the present (A) (Solid contents) contained in the antifouling coating invention can be produced by appropriately employing composition, it is preferred that the orthophosphoric ester be known processes. For example, the antifouling coating com contained in an amount of 1 to 50 parts by weight, especially position can be obtained by Simultaneously or in arbitrary 2 to 40 parts by weight. Sequence adding, to 100 parts by weight of silyl ester copolymer (A) containing constituent units derived from a 0355. When the orthophosphoric ester is contained as the polymerizable unsaturated carboxylic acid silyl ester, 0.02 to plasticizer (I), a coating film with resistance to cracking and 1000 parts by weight of carboxylic acid (B), 1.5 to 1200 peeling can be formed. In Some cases, the consumption of parts by weight of bivalent or trivalent metal compound (C), coating film can be accelerated depending on the combina 0.01 to 50 parts by weight of dehydrating agent (D), 3 to tions and amounts of compounding components. 1400 parts by weight of antifouling agent (E), 0.1 to 700 parts by weight of zinc oxide (F), 0 to 600 parts by weight of elution accelerating component (G), 0.3 to 200 parts by AntiSagging/Antisetting Agent weight of vinyl ether (co)polymer (H), 1 to 50 parts by 0356. The antifouling coating composition maybe loaded weight of plasticizer (I) and appropriate amounts of an with known antisagging/antisetting agents in arbitrary antisagging/antisetting agent, a pigment, a Solvent, etc., and amounts. Examples of Suitable antisagging/antisetting agitating, mixing and dispersing the composition. agents include Salts. Such as Al, Ca and Zn Stearates, leci 0363. It is preferred to prepare the carboxylic acid thinates and alkylsulfonates, polyethylene wax, hydroge exceSS-metal Salt in advance by mixing together a carboxylic nated castor oil wax, polyamide wax, mixtures of these acid (B) and a bivalent or trivalent metal compound (C) waxes, Synthetic particulate Silica and oxidized polyethylene together with an appropriate amount of Solvent. When this wax. Of these, hydrogenated castor oil wax, polyamide wax, advance preparation is effected, the Salt formation can be Synthetic particulate Silica and oxidized polyethylene waX carried on easily and rapidly. Further, when the dehydrating are preferred. Further, use can be made of antisagging/ agent (D) is mixed during the preparation of the above antisetting agents commercially available by the trade exceSS-metal Salt or thereafter, the water generated during names, for example, “Disparlon A-603-20X” and “Dispar the formation of exceSS-metal Salt can be efficiently lon 4200-20', which are produced by Kusumoto Chemicals, removed. Ltd. 0364. The antifouling coating composition of excellent properties according to the present invention can be effi Pigment and Solvent ciently prepared by, after the above operation, adding 0357 Various known organic and inorganic pigments remaining components to be added Simultaneously or in (e.g., titanium white, red iron oxide, organic red pigments arbitrary Sequence, and by agitating, mixing and dispersing and talc) can be used as the pigment in the antifouling the composition. coating composition. In addition, various colorants Such as 0365 More specifically, in method (1), a carboxylic acid dyes maybe incorporated in the antifouling coating compo (B) and a bivalent or trivalent metal compound (C), the Sition. bivalent or trivalent metal compound (C) used in an amount 0358. The cracking resistance of coating film can be of 1.2 equivalents or more in terms of the number of enhanced by the use of pigments with needle, flat and flake equivalents of metal as a constituent of the bivalent or forms. trivalent metal compound (C) per equivalent of carboxyl group of the carboxylic acid (B) as aforementioned, are 0359 Various solvents customarily used in antifouling brought into contact with each other through mixing/stirring paints, Such as aliphatic, aromatic (e.g., Xylene and toluene), or like means to there by form an organic carboxylic acid ketone, ester and ether Solvents, can be incorporated in the exceSS-metal Salt in advance. US 2003/0207962 A1 Nov. 6, 2003 20
0366 Thereafter, the obtained component (composition) EFFECT OF THE INVENTION containing organic carboxylic acid exceSS-metal Salt is 0371. According to the present invention, there can be mixed with other aforementioned various components to be obtained an antifouling coating composition capable of added, including given amounts of dehydrating agent (D) forming an antifouling coating film which exhibits leSS and component (A), and stirred. In this manner, preferably, cracking tendency, excellent adherence So as to ensure leSS there can be obtained the antifouling coating composition peeling tendency and desirably controlled hydrolysis rate So containing organic carboxylic acid exceSS-metal Salt accord as to be excellent in antifouling performance (antifouling ing to the present invention. activity), in particular, antifouling properties in Stationary 0367 Alternatively, in method (2), a carboxylic acid (B) environment or highly fouling environment and long-term and a bivalent or trivalent metal compound (C), the bivalent antifouling properties, which antifouling coating composi or trivalent metal compound (C) used in an amount of 1.2 tion is excellent in Storage Stability, can reduce the amount equivalents or more in terms of the number of equivalents of of Solvent used therein and is excellent in applicability metal as a constituent of the bivalent or trivalent metal (uniform thick film can be formed by one coating operation). compound (C) per equivalent of carboxyl group of the 0372 Further, according to the present invention, there is carboxylic acid (B) as aforementioned, together with a given provided a coating film with the above excellent properties, amount of dehydrating agent (D) are brought into contact and provided a hull or underwater structure covered with the with each other through mixing/stirring or like means to coating film to thereby have the above excellent properties. there by form a component (composition) containing an 0373 Still further, according to the present invention, organic carboxylic acid exceSS-metal Salt, wherein the there is provided an antifouling method wherein the above amount of formed water has been reduced or made nil, in antifouling coating composition is employed to thereby advance. minimize the danger of environmental pollution. 0368. Thereafter, the obtained component (composition) containing organic carboxylic acid exceSS-metal Salt is EXAMPLE mixed with given amounts of aforementioned essential 0374. The present invention will further be illustrated component (A) and various optional components, and below with reference to the following Examples which in no Stirred. In this manner as well, there can preferably be way limit the scope of the invention. In the following obtained the antifouling coating composition containing Examples and Comparative Examples, the term "parts” organic carboxylic acid exceSS-metal Salt according to the means “parts by weight”. present invention. Production Example 1 0369 The thus obtained antifouling coating composition is of the one package type and has excellent Storage Stability. 0375 (Production of silyl (meth)acrylate copolymer Further, the antifouling coating composition Satisfies various (S-1) requirements for performance Such as antifouling paint 0376 100 parts of xylene was charged in a reaction vessel adherence, durability and antifouling properties. equipped with a stirrer, a condenser, a thermometer, a 0370 For example, hulls, marine structures and other dropping device, a nitrogen introduction tube and a heating/ shaped items covered with an antifouling coating film hav cooling jacket, and heated under Stirring at 85 C. in a ing excellent cracking resistance and antifouling properties nitrogen Stream. A mixture of 50 parts of triisopropylsilyl can be obtained by applying the above antifouling coating acrylate, 50 parts of methyl methacrylate and 1 part of composition to the Surface of various shaped items (base 2,2'-aZobisisobutyronitrile as a polymerization initiator was materials), Such as an underwater/floating structure, namely, dropped through the dropping device into the reaction vessel a marine Structure (e.g., plumbing port of a nuclear power while maintaining the above temperature over a period of 2 Station), a sludge diffusion preventive film for use in various hrs. The Stirring was continued at the same temperature for ocean civil works for a bayshore road, an underSea tunnel, 4 hrs. Further, 0.4 part of 2,2'-azobisisobutyronitrile was port facilities, a canal/channel, etc., a marine vessel and a added, and the Stirring was continued at the same tempera fishing gear (e.g., a rope and a fishing net), once or a ture for 4 hrs. Thus, a colorless transparent Solution of silyl plurality of times hardening the applied antifouling coating (meth)acrylate copolymer (S-1) was obtained. composition according to the customary procedure. This 0377 The heating residue (residue after drying in a antifouling coating composition may be directly applied to thermostatic oven set at 105 C. for 3 hrs) from the obtained the Surface of hulls and marine Structures, or applied to the solution of copolymer (S-1) amounted to 51.2% by weight. Surface of hulls and marine Structures precoated with an The viscosity at 25 C. thereof was 408 cps, and the weight undercoating material Such as a rust preventive or a primer. average molecular weight (Mw) and number average Moreover, the antifouling coating composition of the present molecular weight (Mn), measured by GPC, of the copolymer invention may be applied as a top coat for repair to the were 19434 and 6618, respectively. Surface of hulls and marine Structures previously coated with the conventional antifouling paint or the antifouling coating 0378 GPC measurements were performed under the fol composition of the present invention. Although the thickneSS lowing conditions. of the antifouling coating film thus formed on the Surface of 0379 (Conditions for GPC measurement) hulls and marine Structures is not particularly limited, for example, it ranges from about 30 to 150 um for each 0380 Instrument: HLC-8120 GPC manufactured by application. Tosoh Corporation, US 2003/0207962 A1 Nov. 6, 2003 21
0381 Column: Super H2000+H4000 of 6 mm inside tions were changed as Specified in Tables 1 and 2. The diameter and 15 cm, manufactured by Tosoh Corpo properties of these copolymers (Solutions) were also mea ration, Sured in the same manner. 0382 Eluant: THF (tetrahydrofuran), 0388. The results are collectively listed in Tables 1 and 2. 0383) Flow rate: 0.500 ml/min, Comparative Production Examples 1 to 3 0384) Detector: RI, and 0385 Temperature of column thermostatic chamber: 0389 (Production of silyl (meth)acrylate copolymers 40° C. (H-1) to (H-3)) 0390 These copolymers (H-1) to (H-3) were produced in Production Examples 2 to 17 the same manner except that in the preparation of copolymer 0386 (Production of silyl (meth)acrylate copolymers Solution, the dropped copolymerizable monomer formula (S-2) to (S-17)) tions were changed as Specified in Tables 1 and 2. The properties of these copolymers (Solutions) were also mea 0387 These copolymers (S-2) to (S-17) were produced in Sured in the same manner. the same manner except that in the preparation of copolymer Solution, the dropped copolymerizable monomer formula 0391 The results are collectively listed in Tables 1 and 2. TABLE 2 Type of polymer (loadings: parts by weight) S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-8 S-9
Solvent Xylene 1OO 1OO 1OO 1OO 1OO 1OO 1OO 1OO 1OO Dropped triisopropylsilyl acrylate 50 50 40 50 50 65 components tri-n-butylsilyl methacrylate 50 triisobutylsilyl methacrylate 50 di-sec-butylmethylsilyl 45 methacrylate diisopropylmethylsilyl methacrylate methyl methacrylate 50 45 50 55 45 40 3O 45 50 2-methoxyethyl acrylate 5 ethyl acrylate 5 5 10 5 5 5 2-hydroxypropyl acrylate 2-hydroxybutyl acrylate polyethylene glycol monomethacrylate (n = 5) methoxypolyethylene glycol monomethacrylate (n = 45) N-ethoxymethylacrylamide 2,2'-azobisisobutyronitrile 1. 1. 1. 1. 1. 1. 1. 1. 1. Properties heating residue (wt.%) 51.2 SO.1 50.6 49.5 SO.8 49.6 SO.1 50.3 48.9 of product viscosity/25 C. (cps) 408 111 279 364 343 297 335 222 365 GPC measurement Mn 6618 4449 11200 4998 4596 5039 5113 SOO4 4857 Mw 19434 15773 205OO 16229 16049 16987. 16038 17489 18254 Mw/Mn 2.9 3.5 18 3.2 3.5 3.4 3.1 3.5 3.8 Type of polymer (loadings: parts by weight) S-10 S-11 S-12 S-13 S-14 S-15 S-16 S-17
Solvent xylene 1OO 1OO 1OO 1OO 1OO 1OO 1OO 1OO Dropped triisopropylsilyl acrylate 50 50 50 50 50 3O 50 components tri-n-butylsilyl methacrylate 5 triisobutylsilyl methacrylate di-sec-butylmethylsilyl methacrylate diisopropylmethylsilyl 45 methacrylate methyl methacrylate 50 45 45 45 45 45 65 45 2-methoxyethyl acrylate ethyl acrylate 5 2-hydroxypropyl acrylate 5 2-hydroxybutyl acrylate 5 polyethylene glycol 5 monomethacrylate (n = 5) methoxypolyethylene glycol 5 monomethacrylate (n = 45) N-ethoxymethylacrylamide 5 5 2,2'-azobisisobutyronitrile 1. 1. 1. 1. 1. 1. 1. 1. Properties heating residue (wt.%) 50.5 50.7 50.9 50.9 50.9 SO.4 50.5 50.9 of product viscosity/25 C. (cps) 698 264 353 297 374 304 493 466 GPC measurement Mn 5788 5223 5132 5167 5382 3514 6228 5470 Mw 18567 19196 19344 17963 27009 14798 21435 20894 Mw/Mn 3.2 3.7 3.8 3.5 5.0 4.2 3.4 3.8 US 2003/0207962 A1 Nov. 6, 2003 22
0392) 04.05 With respect to the antifouling coating composi tion, the initial Ku value was 90, and the storage stability and TABLE 2 Stationary antifouling performance were both graded as 5. Further, the coating film consumption was 12 um/2 months, Comparative Polymers and the coating film condition was graded as 5. Type of polymer (loadings: parts by weight) H-1 H-2 H-3 0406) The results are collectively listed in Tables 3 to 7. Solvent Xylene 1OO 1OO 1OO 04.07 Initial Ku Dropped triisopropylsilyl acrylate 50 50 0408. The viscosity (Ku value/25° C) of antifouling compo- tri-n-butylsilyl methacrylate 50 ments methyl methacrylate 50 45 50 coating composition immediately after preparation was 2-methoxyethyl acrylate 5 measured by a Stormer Viscometer. 2,2'-azobisisobutyronitrile 1. 1. 1. Proper- heating residue (wt.%) 51.2 SO.1 50.6 04.09 Storage Stability ties of viscosity/25 C. (cps) 408 111 279 product GPC measurement Min 6618 4449 112OO 0410 The storage stability of antifouling coating com Mw 19434 15773 20500 position measured after Storing at room temperature for 2 Mw/Mn 2.9 3.5 18 months is collectively listed in Tables 3 to 7. 0411 Evaluation of storage stability was made on the basis of an increment of viscosity (Ku value at 25 C. 0393 IR measurements were performed under the fol measured by a Stormer Viscometer) exhibited after Storage at lowing conditions. room temperature for two months after the paint preparation 0394 (Conditions for IR measurement) over the Viscosity immediately after the paint preparation. 0395. Instrument: Hitachi infrared spectrophotom 0412 (Criterion for evaluation) eter, model 270-30, manufactured by Hitachi, Ltd., and 0413 5: Viscosity increment is less than 10, 0414. 4: Viscosity increment is in the range of 10 to 0396 Measuring method: KBr cell, coating method. less than 20, 0397) The zinc content measured by chelatometric titra 0415 3: viscosity increment is in the range of 20 to tion was 15.40%. The chelatometric titration was performed less than 30, in the following manner. 0416 2: viscosity increment is 30 or greater, and 0398 (Chelatometric titration) 0417. 1: there is no fluidity, and measuring of Ku 0399. A sample was dissolved in toluene. EDTA was value is impossible. added to the Solution, thereby forming a metal chelate. Back 0418 Furthermore, with respect to the antifouling coat titration of excess EDTA was performed with a solution of ing composition, the Stationary antifouling performance and Zinc chloride by the use of BT as an indicator, thereby consumption rate were evaluated in the following manner. determining a metal content. 0419) The results are collectively listed in Tables 3 to 7. 0400 BT: Eriochrome Black T(sodium 1-(hydroxy 2-naphtholazo)-6-nitro-2-naphthol-4-Sulfate) 0420 Testing of Stationary Antifouling Performance 0421) An epoxy-based zinc-rich primer (content of zinc Example 1 powder in paint film: 80% by weight), a tar epoxy-based anti corrosive paint and a vinyl binder coat were Successively 04.01 (Preparation of antifouling coating composition) applied in this order to a sandblasted steel plate of 100x 0402 2.3 parts by weight of isononanoic acid, 6 parts by 300x2 mm at one-day intervals so that the respective film weight of Zinc oxide and 3 parts by weight of Xylene were thicknesses were 20, 150 and 75 lum, respectively, in the dry charged into the container of a paint Shaker. An appropriate State. Thereafter, the antifouling coating composition to be amount of glass beads were added to the mixture, and tested was applied to the coated Steel plate So that its Shaken for 30 min by the paint Shaker (preliminary disper thickness was 100 um in the dry State, thereby obtaining a Sion). Specimen plate. 0403. Thereafter, 20 parts by weight of copolymer solu 0422 This specimen plate was suspended from a test raft tion (S-1), 44 parts by weight of cuprous oxide, 3 parts by Set off the bay of Nagasaki So that it positioned at an weight of 2-pyridinethiol-1-oxide copper Salt, 2 parts by underwater depth of 1 m. The area of adherence of macro weight of titanium white, 2 parts by weight of anhydrous organisms (barnacle, Serpula, etc.) to the specimen plate was gypsum D-1, 1.5 parts by weight of Disparlon 4200-20, 4 evaluated 24 months later. parts by weight of Disparlon A-603-20X and 9.7 parts by weight of xylene (the amount of Solvent was regulated So 0423 Criterion for evaluation (mark) that the initial Ku value became 85+5) were added to the 0424 5: no adherence, mixture, and all the components were shaken together for 2 hrs (main dispersion). 0425 4: adherence of less than 5%, 0426) 3: adherence of 5% to less than 15%, 04.04 The resultant dispersion was filtered through a 100-mesh filter, thereby obtaining a desired antifouling 0427 2: adherence of 15% to less than 40%, and coating composition. 0428 1: adherence of 40% or more. US 2003/0207962 A1 Nov. 6, 2003 23
0429 Evaluation of Consumption Rate and Coating Film 0442 (2) “Lutonal A-25” Condition 0443 polyvinyl ethyl ether produced by BASF AG, 0430 (Evaluation of consumption rate) having a viscosity of 2.5 to 6.0 Pa's at 23° C. and a 0431. An epoxy-based zinc-rich primer, an epoxy-based specific gravity of 0.96 at 20° C.; anticorrosive paint and a vinyl binder coat were Successively applied in this order at one-day intervals to a disk-shaped 0444 (3) “Rosin solution” sandblasted plate of 300 mm diameter and 3 mm thickness 0445) 50% solution of WW rosin in xylene; so that the respective film thicknesses were 20, 150 and 50 tim, respectively, in the dry State. The obtained coated plate 0446 (4) “Copper naphthenate solution” was dried indoors for 7 days. Thereafter, the antifouling coating composition to be tested was radially applied onto 0447 solution of copper naphthenate in Xylene, hav the coated plate in the radius direction from the center ing a copper content in Solution of 8%, thereof by the use of an applicator with a clearance of 500 0448 (5) “Soluble anhydrous gypsum D-1” tim, thereby obtaining a specimen plate. This specimen plate was Secured to a motor and rotated in a thermostatic bath 0449 IIICaSO white powder of 15 um average filled with 25 C. seawater at a peripheral speed of 15 knots particle diameter, produced by Noritake Co., Ltd., for 2 months. The consumption rate (decrease of coating film thickness) in the vicinity of the circumference of 0450 (6) “Disparlon 4200-20” Specimen plate was measured. 0451 oxidized polyethylene wax (20% xylene 0432. Furthermore, the condition of coating film at the paste), produced by Kusumoto Chemicals, Ltd.; and time of measuring the decrease of coating film thickneSS was evaluated by Visual inspection according to the following 0452 (7) “Disparlon A603-20X” criterion. 0453 fatty acid amide wax (20% xylene paste), 0433 (Criterion for evaluation) produced by Kusumoto Chemicals, Ltd. 0434 5: no abnormality is observed on the coating Examples 2 to 38 and Comparative Examples 1 to film, 10 0435) 4: Some tiny cracks are observed, 0436 3: tiny cracks are observed overall, 0454) (Preparation of antifouling coating compositions) 0437. 2: Some clear cracks are observed, and 0455 Antifouling coating compositions were prepared in 0438) 1: clear cracks are observed overall. the same manner as in Example 1, except that the formula 0439 Component nomenclatures employed in Tables 3 to tions thereof were changed as specified in Tables 3 to 7. 7 are as follows: 0456 With respect to the obtained antifouling coating 0440 (1) “Toyoparax 150” compositions, not only the Storage Stability thereof but also 0441 chlorinated paraffin produced by ToSoh Cor the Stationary antifouling performance and consumption rate poration, having 14.5 carbon atoms on the average, of antifouling coating films formed from the antifouling a chlorine content of 50%, a viscosity of 12ps at 25 coating compositions were evaluated. C. and a specific gravity of 1.25 at 25 C.; 0457. The results are collectively listed in Tables 3 to 7.
TABLE 3
Example
2 3 4 5 6 7 8 9 1O 11 12 Formulation (loadings: parts by weight)
Prelim. isononanoic acid 2.3 5.0 2.3 5.0 2.3 5.0 1.6 3.2 S.O 5.0 5.0 dispersion versatic acid 1.6 components rosin Zinc oxide 6.O 7.7 6.O 7.7 6.O 7.7 1.O 2.O 3.0 7.7 7.7 6.5 xylene 3.0 6.O 3.0 6.O 3.0 6.O 3.0 4.0 6.O 6.O 6.O 2.O anhydrous gypsum D-1 3.0 2.O 3.0 2.O 3.0 1.O 2.O 3.0 1.O 1.O 1.O Main dispersion components
type of copolymer soln. (see Tables1-2) S-1 S-2 S-2 S-3 S-4 S-5 S-5 S-5 S-5 S-5 S-5 amt. of copolymer Soln. added 13.O 20.O 13.O 20.O 13.O 20.O 20.O 130 13.O 13.O 20.O Toyoparax 150 4.0 1.O Lutonal A-25 2.O US 2003/0207962 A1 Nov. 6, 2003 24
TABLE 3-continued Example
1. 2 3 4 5 6 7 8 9 11 12 antifouling cuprous Oxide 44.0 44.0 44.0 44.0 41.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 agent 2-pyridinethiol-1-oxide 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Cusalt 2-pyridinethiol-1-oxide Zn salt 4,5-dichloro-2-n-octyl isothiazolin-3-one 2,4,5,6-tetrachloroiso phthalonitrile 2-methylthio-4-t-butyl amino-6-cyclopropyl amino-s-triazine N-(2,4,6-trichlorophenyl) maleimide N,N-dimethyldichloro phenylurea pyridine-triphenylborane copper rhodanate titanium white 2.0 2.O 2.O 2.O 2.O 2.O 2.O 2.0 2.O 2.O 2.0 2.O anhydrous gypsum D-1 2.0 2.O 2.0 0.5 Zinc oxide 5.5 5.1 4.7 talc F2 Disparlon 4200-20 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Disparlon A603-20X 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 xylene 9.7 7.8 9.7 7.8 8.2 6.8 9.4 8.2 6.8 6.7 7.8 9.9 total 97.5 97.O 97.5 97.0 97.0 96.O 96.O 99.0 96.O 96.9 99.0 96.O Evalua- initial Ku 90 86 tion result storage stability 5 stationary antifouling 5 performance consumption (u?2 month-s) 12 6 condition of coating film 5
0458)
TABLE 4 Example
13 14 15 16 17 18 19 21 22 23 24 Formulation (loadings: parts by weight)
Prelim. isononanoic acid 5.0 5.0 5.0 5.0 5.0 5.0 dispersion versatic acid 3.2 5.1 5.1 5.1 5.2 components rosin 4.2 Zinc oxide 6.O 7.6 7.6 8.6 7.5 6.7 7.7 7.7 7.7 7.7 7.7 7.7 Xylene 4.0 6.O 6.O 6.O 6.0 4.6 6.O 6.O 6.O 6.O 6.O 6.O anhydrous gypsum D-1 1.O 1.O 1.O 1.O 1.O 1.O 1.O 1.O 1.O 1.O 1.O 1.O Main dispersion components type of copolymer soln. (see Tables 1-2) S-5 S-5 S-5 S-7 S-5 S-5 S-6 S-7 S-8 S-9 S-10 S-11 amt. of copolymer Soln. added 2O.O 13.O 130 13.O 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 Toyoparax 150 O 4.0 4.0 Lutonal A-25 2.O Antifouling cuprous Oxide 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 agent 2-pyridinethiol-1-oxide 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Cusalt 2-pyridinethiol-1-oxide Zn salt 4,5-dichloro-2-n-octyl isothiazolin-3-one 2,4,5,6-tetrachloroiso phthalonitrile 2-methylthio-4-t-butyl amino-6-cyclopropyl US 2003/0207962 A1 Nov. 6, 2003 25
TABLE 4-continued Example
13 14 15 16 17 18 19 21 22 23 24 amino-s-triazine N-(2,4,6-trichlorophenyl) maleimide N,N-dimethyldichloro phenylurea pyridine-triphenylborane copper rhodanate titanium white 2.0 2.O 2.O 2.O 2.O 2.O 2.O 2.0 2.O 2.O 2.0 2.O anhydrous gypsum D-1 0.5 0.5 0.5 0.5 O.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Zinc oxide talc F2 Disparlon 4200-20 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Disparlon A603-20X 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 xylene 7.8 9.5 7.8 6.3 6.3 10.6 7.3 7.3 7.3 7.8 7.8 total 97.0 97.2 97.5 95.O. 940 95.1 95.0 95.0 95.0 99.5 99.5 Evalua initial Ku 84 tion result storage stability stationary antifouling performance consumption (u?2 months) condition of coating film
0459)
TABLE 5 Example
25 26 27 28 29 31 32 33 34 35 36 Formulation (loadings: parts by weight)
Prelim. isononanoic acid 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 dispersion versatic acid components rosin Zinc oxide 7.7 7.7 7.7 7.7 7.7 7.7 7.7 7.7 7.7 7.7 7.7 7.7 Xylene 6.O 6.O 6.O 6.O 6.0 6.O 6.O 6.O 6.O 6.O 6.O 6.O anhydrous gypsum D-1 1.O 1.O 1.O 1.O 1.O 1.O 2.O 2.0 2.O 2.O 2.0 2.O Main dispersion components type of copolymer soln. (see Tables 1-2) S-12 S-13 S-14 S-15 S-16 S-17 S-5 S-5 S-5 S-5 S-5 S-5 amt. of copolymer Soln. added 13.0 13.O 130 13.O 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 Toyoparax 150 Lutonal A-25 antifouling cuprous Oxide 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 agent 2-pyridinethiol-1-oxide 3.0 3.0 3.0 3.0 3.0 3.0 3.0 2.O 2.0 2.O Cusalt 2-pyridinethiol-1-oxide 1.O Zn salt 4,5-dichloro-2-n-octyl 4.0 3.0 isothiazolin-3-one 2,4,5,6-tetrachloroiso 6.O phthalonitrile 2-methylthio-4-t-butyl 3.0 amino-6-cyclopropyl amino-s-triazine N-(2,4,6-trichlorophenyl) 3.0 maleimide antifouling N,N-dimethyldichloro 3.0 agent phenylurea pyridine-triphenylborane copper rhodanate titanium white 2.0 2.O 2.O 2.O 2.O 2.O 2.O 2.0 2.O 2.O 2.0 2.O anhydrous gypsum D-1 0.5 0.5 0.5 0.5 O.5 0.5 Zinc oxide talc F2 US 2003/0207962 A1 Nov. 6, 2003 26
TABLE 5-continued Example
25 26 27 28 29 30 31. 32 33 34 35 36 Disparlon 4200-20 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 15 1.5 1.5 1.5 Disparlon A603-20X 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 xylene 7.3 7.3 7.3 7.3 7.3 7.3 7.3 8.3 8.8 8.3 8.3 8.3 total 95.0 95.0 95.0 95.0 95.0 95.0 97.5 99.5 10O.O 98.5 98.5 98.5 Evalua- initial Ku 82 82 84 84 84 85 82 83 85 85 86 85 tion result storage stability 5 5 5 5 5 5 5 5 5 5 5 5 stationary antifouling 5 5 5 5 5 5 5 5 5 5 5 5 performance consumption (u?2 month-s) 49 45 50 45 39 55 43 43 44 45 45 42 condition of coating film 5 5 5 5 5 5 5 5 5 5 5 5
0460) TABLE 6-continued TABLE 6 Example Example Formulation (loadings: parts by weight) 37 38 Formulation (loadings: parts by weight) 37 38 N-(2,4,6-trichlorophenyl)maleimide Prelim. isononanoic acid 5.0 5.0 N,N-dimethyldichlorophenylurea dispersion versatic acid pyridine-triphenylborane 9.O components rosin copper rhodanate 1O.O Zinc oxide 7.7 7.7 titanium white 2.O 2.O Xylene 6.O 6.O anhydrous gypsum D-1 2.O 2.O anhydrous gypsum D-1 Main dispersion components Zinc oxide 13.0 13.0 o talc F2 7.0 7.0 type of copolymer soln. (see Tables 1-2) S-5 S-5 Disparlon 4200-20 1.5 1.5 amt. of copolymer Soln. added 3O.O 3O.O Disparlon A603-20X 4.0 4.0 Toyoparax 150 Xylene 9.8 9.3 Lutonal A-25 antifouling cuprous Oxide total 97.0 97.5 agent 2-pyridinethiol-1-oxide Cu salt Evaluation initial Ku 87 88 2-pyridinethiol-1-oxide Zn salt result storage stability 5 5 4,5-dichloro-2-n-octylisothiazolin- stationary antifouling performance 5 5 3-one consumption (u?2 months) 31 28 2,4,5,6-tetrachloroisophthalo- condition of coating film 5 5 nitrile 2-methylthio-4-t-butylamino-6- cyclopropylamino-s-triazine 0461) TABLE 7 Comparative Example Formulation (loadings: parts by weight) 1. 2 3 4 5 6 7 8 9 1O copolymer S-1 26 soln. S-2 26 2O 13 2O 13 S-3 2O 2O 2O 2O isononanoic acid 3 6.5 3 K-3 (1:1 equiv. ratio) 4.3 9.5 4.3 versatic acid 3 rosin (WW rosin) 3 Toyoparax 150 4 4 4 4 titanium white 2 2 2 2 2 2 2 2 2 2 cuprous oxide 45 45 45 45 45 45 42 42 42 42 Zinc oxide 6 6 6 6 6 6 6 6 6 6 copper pyrithione 3 3 3 3 3 3 3 3 3 3 anhydrous gypsum D-1 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. Disparlon 4200-20 1.5 1.5 1.5 1.5 1.5 1.5 1. 1.5 1.5 1.5 Disparlon A603-20X 4 4 4 4 4 4 4 4 4 4 xylene 11.5 11.5 14.5 18 13.2 15 13.5 12.2 13.5 13.5
total 1OO 100 100 1 OO 100 100 1 OO 100 100 100 Evaluation initial Ku 86 86 92 94 92 94 96 95 96 92 US 2003/0207962 A1 Nov. 6, 2003 27
TABLE 7-continued Comparative Example Formulation (loadings: parts by weight) 1. 2 3 4 5 result storage stability 5 5 3 1. 3 stationary antifouling 1. 1. 1. 2 1. performance consumption (u?2 mo-nths) 4 5 13 24 14 condition of coating 5 5 3 1. 3 film
0462. As apparent from Tables 3 to 7, it was recognized polymerizable unsaturated carboxylic acid silyl ester include that the use of carboxylic acid (B) in combination with the constituent units derived from a silyl (meth)acrylate which bivalent or trivalent metal compound (C) reduced the con are represented by the formula: Sumption rate of coating film. What is claimed is: 1. An antifouling coating composition comprising: (I) (A) a silyl ester copolymer containing constituent units CH2 derived from a polymerizable unsaturated carboxylic acid Sillyl ester, CRCOOSiRRR (B) a carboxylic acid, (C) a bivalent or trivalent metal compound, and wherein R' represents hydrogen or a methyl group; and R. (D) a dehydrating agent. RandR' may be identical with or different from each other, 2. The antifouling coating composition as claimed in and each thereof represents any of a hydrogen atom, an alkyl claim 1, wherein the bivalent or trivalent metal compound group, a cycloalkyl group, a Substituted or unsubstituted (C) is contained in an amount of 1.2 equivalents or more, in phenyl group and an alkylsilyloxy group. terms of the number of equivalents of metal as a constituent 10. The antifouling coating composition as claimed in of the bivalent or trivalent metal compound (C), per equiva claim 9, wherein in the formula (I), R represents a branched lent of carboxyl group of the carboxylic acid (B). alkyl group or a cycloalkyl group. 3. The antifouling coating composition as claimed in 11. The antifouling coating composition as claimed in claim 1 or 2, wherein the bivalent or trivalent metal com claim 1, wherein the silyl ester copolymer (A) contains pound (C) is a bivalent metal compound. constituent units (a) derived from a polymerizable unsatur 4. The antifouling coating composition as claimed in ated carboxylic acid silyl ester and constituent units (b) claim 3, wherein the bivalent or trivalent metal compound derived from a (meth)acrylate having a polar group. (C) is a compound of at least one metal Selected from the 12. The antifouling coating composition as claimed in group consisting of Zinc, copper, magnesium, calcium and claim 11, wherein the constituent units (b) derived from a barium. (meth)acrylate having a polar group are constituent units 5. The antifouling coating composition as claimed in represented by the formula: claim 1, wherein the carboxylic acid (B) is a resin acid or resin acid derivative containing at least one carboxylic acid Selected from the group consisting of abietic acid, dehy (II) droabietic acid, dihydroabietic acid, tetrahydroabietic acid, noragathic acid, agathenedicarboxylic acid, an agathenedi CH2 carboxylic acid monoalkyl ester, Secodehydroabietic acid CRCOZR6 and isomers thereof. 6. The antifouling coating composition as claimed in claim 1, wherein the carboxylic acid (B) is at least one organic acid Selected from the group consisting of isononanoic acid, Versatic acid, naphthenic acid, oleic acid, wherein R represents a hydrogen atom or a methyl group; linoleic acid, linolenic acid, tall oil fatty acid and Soybean oil and Z represents an oxygen atom or a group of the fatty acid. formula -NR", provided that: 7. The antifouling coating composition as claimed in when Z is an oxygen atom, R represents a Substituted claim 1, wherein the dehydrating agent (D) is an inorganic or unsubstituted hydroxyalkyl group, hydroxycy dehydrating agent. cloalkyl group, polyalkylene glycol group of the 8. The antifouling coating composition as claimed in formula -(RO)nH (wherein R represents an alky claim 1, wherein the dehydrating agent (D) is contained in lene group, and n is an integer of 2 to 50) or an amount of 0.15 to 50 equivalents per equivalent of alkoxypolyalkylene glycol group of the formula carboxyl group of the carboxylic acid (B). -(RO)nR' (wherein R* represents an alkylene 9. The antifouling coating composition as claimed in group, R represents an alkyl group, and n is an claim 1, wherein the constituent units (a) derived from a integer of 1 to 100), and US 2003/0207962 A1 Nov. 6, 2003 28
when Z is a group of the formula-NR, R represents wherein R" represents a hydrogen atom or a methyl an alkyl group unsubstituted or Substituted with any group; each of R'' and R' independently represents a of a halogen, a hydroxyl group, an amino group, a branched alkyl or cycloalkyl group having 3 to 10 Substituted amino group, an acyl group and an carbon atoms; and R' represents a linear alkyl group alkoxy group, and R represents a hydrogen atom. having 1 to 10 carbon atoms, a branched alkyl or 13. The antifouling coating composition as claimed in cycloalkyl group having 3 to 10 carbon atoms, or a claim 1, wherein the silyl ester copolymer (A) is a copoly Substituted or unsubstituted phenyl group having 6 to mer containing: 10 carbon atoms or trimethylsilyloxy group. 14. The antifouling coating composition as claimed in silyl (meth)acrylate constituent units (a-1) represented by claim 1, further comprising an antifouling agent (E). the formula: 15. The antifouling coating composition as claimed in claim 14, wherein copper or a copper compound (E1) is contained as the antifouling agent (E). (I-a) 16. The antifouling coating composition as claimed in claim 14, wherein an organic antifouling agent compound CH2 (E2) excluding an organocopper compound is contained as CR 10COOSiR11R12R 13 the antifouling agent (E). 17. The antifouling coating composition as claimed in claim 1, further comprising Zinc oxide (F) as a body pigment or color pigment, said Zinc oxide (F) contained in an excess wherein R" represents a hydrogen atom or a methyl amount up to 5000 equivalents per equivalent of carboxyl group; each of R'' and R' independently represents a group of the carboxylic acid (B). linear alkyl group having 1 to 10 carbon atoms, or a 18. The antifouling coating composition as claimed in Substituted or unsubstituted phenyl group or trimeth claim 1, further comprising an elution accelerating compo ylsilyloxy group; and R' represents a cyclic or acyclic, nent (G). branched or unbranched alkyl group having 1 to 18 19. An antifouling coating film formed from the antifoul carbon atoms, or a Substituted or unsubstituted phenyl ing coating composition as claimed in any of claims 1 to 18. group having 6 to 10 carbon atoms or trimethylsilyloxy 20. A marine vessel, an underwater Structure, a fishing group, and gear or a fishing net, having a Surface covered with the silyl (meth)acrylate constituent units (a-2) represented by antifouling coating film formed from the antifouling coating the formula: composition claimed in any of claims 1 to 18. 21. A method of rendering antifouling a marine vessel, an underwater Structure, a fishing gear or a fishing net, which (I-b) comprises applying the antifouling coating composition claimed in any of claims 1 to 19 to a Surface of base material of a marine vessel, an underwater Structure, a fishing gear or CH a fishing net and drying the applied antifouling coating CR10COOSiR1R15R 16 composition So that a formed antifouling coating film covers the base material Surface.